For the first time in five years the El Clasico rivals face off in the curtain-raising fixture, with both aiming to claim first blood ahead of what should be another entertaining season.
After falling short in La Liga and the Champions League last time out, victory over Alaves in the domestic cup final to see out the season was barely enough to salvage the Catalan giants' underwhelming campaign.
It did at least give boss Luis Enrique a chance to bow out with a smile, lifting a ninth major honour in his three years at the helm, but there was certainly a sense that a change of direction was required at Camp Nou.
Barca did not wait long to officially unveil Ernesto Valverde as their new boss, ushering in a new era in Catalonia - one supporters will hope proves just as successful as both Enrique and predecessor Pep Guardiola's on the whole.
One bad season should not be enough to write Barcelona off completely, though the loss of one of a handful of true superstars in their ranks has certainly rocked them on the eve of the campaign, with Neymar departing for Paris Saint-Germain in a record £198m transfer.
That shock exit has left Valverde scrambling for new recruits somewhat, so far missing out on his two top targets in Ousmane Dembele and Philippe Coutinho who, should their valuations be met, will likely take up all of the windfall received from Neymar's sale.
New signings are unlikely to arrive before this double-header against Madrid, however, meaning that Valverde will have to make do with just the one high-profile signing - Nelson Semedo joining earlier this summer in a £30.5m deal, while Gerard Deulofeu has rejoined permanently and Marlon Santos is now a first-team fixture after impressing at the tail end of 2016-17.
Valverde does not need any telling about the pressure he is under to bring trophies back to Camp Nou, of course, having spent a couple of years here as a player, but this is a different beast entirely compared to his previous jobs both at home and abroad.
The former Athletic Bilbao chief has made a positive start, seeing off Juventus, Manchester United and Madrid in the United States, before being held by Gimnastic and then comfortably beating Chapecoense in an emotional friendly on Monday evening - five different players registering in that one.
Far too often last term Barca slipped up against the so-called lesser lights, dropping points against Alaves, Celta Vigo, Real Sociedad, Villarreal, Real Betis, Deportivo La Coruna and Malaga, though Valverde will surely have little trouble motivating his players for this mouthwatering opener.
Recent form: WWWWDW
For all the accusations of Zinedine Zidane simply being in the right place at the right time, the Frenchman - equally as successful during his playing days - achieved something at the Bernabeu last term that no other man has managed since 1958.
It had been almost 60 years since Los Blancos last reigned supreme in both Spain and Europe, withstanding the pressure to hold off Barcelona in La Liga and eventually crushing Juventus 4-1 in the Champions League final to become the first side to retain the trophy in its current guise.
The big question now is where does Zidane go from here? There is the small matter of a treble, of course, having crashed out of the Copa del Rey at the quarter-final stage to Celta Vigo last time out in a rare low for the rookie boss, while simply matching last term's success will also be a huge achievement in itself.
Zidane has, it must be remembered, won two Champions Leagues, one La Liga, a couple of UEFA Super Cups and the FIFA Club World Cup just for good measure. All this and he was only appointed as first-team manager 19 months ago.
Madrid only lost five games throughout the 2016-17 season, culminating in their victory over Juventus in Cardiff to strengthen their tag as the world's best side at this moment in time.
There is an argument to be had that Los Blancos are slightly weaker than a few months back, though, having allowed Danilo, Alvaro Morata and James Rodriguez - three players who all played a part in last term's success in some way - to move on, while only Theo Hernandez and Dani Ceballos have been brought in.
Talented they may be, but neither is seen as a true Galactico and Zidane will surely be eyeing up a move for AS Monaco's teen sensation Kylian Mbappe, who is just about the hottest property on the market right now.
Even without any big-name arrivals the capital club are still backed as title favourites which, if their UEFA Super Cup win over Man United earlier this week is anything to go by, is a smart move on the bookies' behalf. Do not bet against Zidane making it a clean sweep this time around.
Recent form: WLLLWW
In the absence of a world-class talent to partner Luis Suarez and Lionel Messi in the frontline, Valverde is likely to stick with Deulofeu for this one should be be deemed fit enough after limping off last time out.
The only absentee for Zidane is Jesus Vallejo, though it is unknown whether star man Cristiano Ronaldo will start at Camp Nou after a disrupted summer programme due to his Confederations Cup participation.
Incredibly, Luka Modric will sit this one out thanks to a red card picked up against Atletico Madrid in this competition three years ago, but he is free to play the second leg next Wednesday at the Bernabeu.
Barcelona possible starting lineup:
Ter Stegen; Vidal, Pique, Umtiti, Alba; Iniesta, Busquets, Rakitic; Messi, Suarez, Deulofeu
Real Madrid possible starting lineup:
Navas; Carvajal, Varane, Ramos, Marcelo; Kroos, Casemiro, Isco; Bale, Benzema, Ronaldo
These great rivals have met on 267 previous occasions in all competitions, stretching back to the first meeting in 1929 when Madrid came out on top 2-1 in the Spanish top flight.
Barcelona have the better record overall, however, winning 111 to Los Blancos' 97, including a dramatic 3-2 victory the last time they faced off at the Bernabeu in April - Messi, not for the first time in this famous fixture, the hero on that occasion.
They have met 12 times in this competition, meanwhile, with Real winning six of those and losing four. Barca have failed to pick up an away win during that time.
Barcelona are the most-successful side in the Supercopa de Espana, winning it 12 times in all and finishing runners-up a further nine times. The Catalan giants certainly have the pedigree and, with Madrid having had to travel to Skopje in midweek for a tough UEFA Super Cup tie against Man United, they may just have the slight advantage for this first leg on home soil.