Veteran star strikers Robert Lewandowski and Karim Benzema both hit doubles on Sunday in contrasting victories for Barcelona and LaLiga leaders Real Madrid.
Lewandowski scored twice for the second game in a row as Jules Kounde made his debut as Barcelona cruised past Valladolid 4-0.
In the late game on Sunday, Real Madrid struggled for 88 minutes at Espanyol. With the scores tied and time running out, Benzema put Real ahead before sealing a 3-1 victory after 10 eventful added minutes.
Real saved their perfect start to the season and climbed back to the top of the table on nine points after three games, ahead of Real Betis on goal difference.
Barcelona rose to third, two points further back.
"To have Lewandowski in your team is a blessing," said Barca coach Xavi Hernandez.
"He's an extraordinary player. Spectacular. A natural leader. It's a blessing to have him with us, it's marvellous.
"He's a model, a born worker. He's humble, he works for the team, he helps the coaching staff, he makes the difference."
At the Camp Nou, Xavi handed Kounde his first start after the club was finally able to register the France defender they signed from Sevilla last month for a reported 50 million euros ($49.8 mn).
Lewandowski hit the post with an early header.
Pedri then spotted the run of Raphinha in behind but the Brazilian was thwarted by goalkeeper Jordi Masip, who was well beaten moments later when Ousmane Dembele's venomous shot clipped the crossbar.
Barca's pressure told after 24 minutes as Raphinha whipped in a teasing cross which a gambling Lewandowski stabbed home.
A marauding Dembele tested Masip from range, and then created the second for Pedri by rolling a perfectly-weighted ball for the midfielder to bury on the stroke of halftime.
Lewandowski all but put the game beyond reach on 64 minutes, running onto a pass from Dembele and cleverly backheeling past Masip with the help of a deflection off Joaquin Fernandez.
Valladolid nearly pulled one back but Marc-Andre ter Stegen saved well from Oscar Plano and Kounde stuck out a leg on the line to keep out the follow-up effort from Roque Mesa.
Barca grabbed a fourth in stoppage time as Roberto volleyed home after Lewandowski was denied a hat-trick after Masip, a former Barcelona player, tipped his shot onto the bar.
'WE WERE QUITE SLOW'
In the late game, Vinicius Junior ran on to a sharp diagonal pass in the 12th minute to slide the ball into the far corner and give Real the lead.
Espanyol fought back. Joselu levelled after 43 minutes. He burst through and when Thibaut Courtois saved his first thump at goal and the ball bounced off Eder Militao, the Espanyol striker beat both Real players to the ball and scuffed it in.
Both teams had chances in the second half before Benzema, as so often in the last year, decided the game. After a quiet game, he found space at the far post with two minutes left, met Rodrygo's cross and volleyed home from cose range.
Deep into frantic added time, Espanyol goalkeeper Benjamin Lecomte, charged out of his box to stop a Real attack received a red card for a foul on Dani Ceballos.
Benzema fired home the free kick.
"We were quite slow," said Real coach Carlo Ancelotti. "We had difficulty managing the intensity of the match."
Villarreal dropped their first points of the season in a 0-0 draw at Getafe as Unai Emery's side saw the award of a penalty overturned following a VAR review in the dying stages.