Gareth Bale had a bittersweet debut for Real Madrid on Saturday following his world record transfer, as he scored but couldn't prevent his new team from drawing 2-2 at Villarreal.
Other than Bale's goal in the 38th minute, Madrid were outplayed in the first half and only Diego Lopez's goalkeeping kept it 1-1 by halftime after Ruben "Cani" Garcia beat him in the 21st.
After an exhausted Bale was substituted in the 62nd minute, Cristiano Ronaldo hit off the break two minutes later to put Madrid in front.
But Cani's hard strike led to Giovani Dos Santos pulling Villarreal even in the 70th.
Alexis Sanchez scored a winner in the fourth minute of stoppage time as Barcelona claimed a slightly fortunate 3-2 victory over winless Sevilla to maintain their 100 per cent record at the top of La Liga.
Lionel Messi forced his way through the defence by sheer force of will and pulled the ball back with Beto's parry pounced on by Alexis, who fired the ball home for the winner.
Dani Alves had put the hosts ahead in the 36th minute only for the referee to controversially disallow Ivan Rakitic's headed goal when there appeared to be nothing wrong with it.
Gallingly for Sevilla, Messi doubled the lead in the 75th minute with a well-crafted goal. Cesc Fabregas' pass to Neymar at the right of the area was in turn passed first-time by the Brazilian across the box with Messi firing high into the centre of the net.
However, Rakitic pulled one back and Sevilla appeared to have earned a draw with a last-minute volley from Coke, only for Alexis to break their hearts at the end of stoppage time.
Atletico Madrid made it four wins in a row to start the campaign after making light work of Almeria in a 4-2 win.
David Villa got the scoring under way by netting with a quarter of an hour gone, before Diego Costa's penalty doubled the hosts' advantage.
Rodri halved the deficit before half-time, but Atleti were far superior in the second period, with Tiago Mendes and Raul Garcia getting in on the act, before Alex Vidal got a late consolation goal.
Levante played out their second home goalless draw of the new season against Real Sociedad.
Both sides hit the crossbar in the second half, Carlos Vela first of all from six yards, before home midfielder Papakouli Diop curled a free-kick against the frame late on.