The Brazilian had been left out of the starting line-up after his exertions in captaining his country for the first time in wins over Colombia and Ecuador in the past week, but made the difference in a tight contest when he slotted home from Lionel Messi’s pass 11 minutes from time.
And the two combined once more five minutes later as this time Messi breezed past three Athletic defenders before cutting the ball back for Neymar to side-foot home.
Barca remain at the top of the table, five points clear of La Liga champions Atletico Madrid and six ahead of Real Madrid with both sides from the capital to face off at the Santiago Bernabeu later on Saturday.
“Messi is the best in the world. He is a star and I am improving with him,” Neymar told Canal Plus.
“I am very happy with the game today. It went perfectly with the two goals.
“We knew we would suffer a little bit, but we managed to remain tight at the back and then went onto win the game.”
Enrique was also quick to laud the impact made by Messi in creating both goals, as he also did for Sandro’s winner at Villarreal two weeks ago.
“It is evident that he is best in the world in any attacking aspect,” he said.
“This version of Messi helps us a lot because he is a game changer. He does things in training that you can’t imagine, things I haven’t even seen on the Playstation.”
Fresh from making his debut with Spain in a 5-1 thrashing of Macedonia on Monday, 19-year-old Munir El Haddadi once again started ahead of Neymar and was a constant threat despite not having his best day in front of goal.
Munir’s first opening of the day came 20 minutes in when he collected Messi’s pass and turned Oscar de Marcos with ease, but then fired wastefully over with just Gorka Iraizoz to beat.
Athletic were coping comfortably with Barca in the final third, though, and threatened themselves when the excellent Ander Iturraspe broke into the box but his shot lacked the power to trouble Claudio Bravo.
Barca upped the pressure on the Athletic goal just before half-time as Iraizoz did well to parry Ivan Rakitic’s fierce low drive before spreading himself to block from Munir at point-blank range as the youngster latched onto another Messi assist.
Munir thought he had broken the deadlock at the start of the second period as he swept home from close range, but was this time denied by the offside flag as he failed to time his run.
Iraizoz was on top form once more to turn Jordi Alba’s low drive behind and hold a powerful header from Munir, but Neymar’s entrance just after the hour mark gave Barca the extra touch of class they needed to punish the Basques.
Aymeric Laporte’s wayward pass was picked off by Sergio Busquets and he fed Messi before the Argentine freed Neymar in behind the Athletic defence to roll home his first goal of the season.
Messi played the role of provider once more six minutes from the end as he floated down the right wing and pulled the ball back for the unmarked Neymar to slot home.
Both sides’ attentions will now turn to Champions League action on Wednesday as Barca host Cypriots APOEL Nicosia and Athletic welcome Shakhtar Donetsk to the new San Mames in their first group stage game in the Champions League for 16 years.