Barcelona will hope for a more favourable result against Athletic Bilbao at the third time of asking, while Rafael Benitez takes control of Real Madrid competitively for the first time as the two great rivals start the latest battle for La Liga supremacy this weekend.
Luis Enrique's Barca swept aside all comers en route to a stunning La Liga, Copa del Rey and UEFA Champions League treble last season, with Lionel Messi, Neymar and Luis Suarez scoring a scarcely believable record 122 goals in all competitions.
However, the Catalan club may travel to San Mames with some trepidation having lost 5-1 on aggregate to Bilbao in the Supercopa de Espana.
That included a 4-0 loss at Athletic just five days ago, while the return leg saw Gerard Pique sent off for insulting a linesman, which landed him a four-match ban.
However, Barca won at San Mames twice last season and they will be keen to set an early marker in what is likely to be another tussle with Clasico rivals Real for the title.
Real won the Copa and Champions League in the 2013-14 campaign, but a failure to retain those trophies and finishing second to Barca ultimately cost Carlo Ancelotti his job.
Benitez knows the pressure will be on to deliver from the off against newly promoted Sporting Gijon and the Spaniard will hope that Cristiano Ronaldo – who scored an incredible 48 league goals that term – can continue to shine to dispel rumours of a spat between the two.
Mateo Kovacic has arrived from Inter to try to add more spark in midfield, but key for Real will be to ensure cohesion between front three Ronaldo, Karim Benzema and Gareth Bale – the latter looking to rebound from a difficult second season in the Spanish capital.
Sevilla, Atletico Madrid and Valencia are the usual suspects attempting to shake things up at the top.
Europa League winners Sevilla have added the likes of Ciro Immobile, Yevhen Konoplyanka and Adil Rami during the close-season and Unai Emery's men kick off the league at Malaga on Friday.
Atletico proved that Barca and Real can be beaten by winning the league in 2013-14 and much will be expected of Jackson Martinez following his arrival from Porto. The striker could get his first competitive outing in an Atleti shirt against promoted side Las Palmas.
Valencia's preparations have been disrupted by speculation over the future of centre-back Nicolas Otamendi – who looks set to join Manchester City – and a tricky opener at Rayo Vallecano awaits Nuno Espirito Santo's side.
David Moyes starts his first full season in charge of Real Sociedad looking to push towards a return to Europe having finished 12th last term and they visit Deportivo La Coruna on Saturday, while Espanyol take on a Getafe side led by Fran Escriba for the first time.
Eibar will look to make the most of their Liga reprieve, having been allowed to stay in the top flight due to Elche's demotion. Jose Luis Mendilibar replaced former coach Gaizka Garitano in the close-season and first up on Monday is Granada, who finished above Eibar only on a better head-to-head record last term.
Other matches see Europa League qualifiers Villarreal travel to Real Betis, while Levante host Celta Vigo