Real Madrid remain just two points behind Barca at the top of the table as goals from Sergio Ramos, James Rodriguez and Cristiano Ronaldo secured a 3-1 win over Malaga despite a rare missed penalty from Ronaldo.
However, victory came at a cost for the European champions as Gareth Bale and Luka Modric hobbled off with injuries just days before their decisive Champions League quarterfinal clash with Atletico Madrid.
Luis Suarez got Barca off to a flying start as he slotted home the opener after just 54 seconds from Messi's through ball.
Valencia then went onto enjoy the majority of the chances, but they were left to rue Dani Parejo's missed penalty in the first half.
And Messi made sure of all three points with the final kick of the game after Diego Alves had saved his initial effort.
"400 goals with Barcelona. Hopefully I can score many more!" Messi posted on his official Facebook page.
"But the most important thing was that we won three points in a very difficult match."
Defeat, meanwhile, leaves Valencia now four points adrift of third-placed Atletico Madrid, who beat Deportivo la Coruna 2-1 thanks to a double from Antoine Griezmann.
"We played very well in the first-half and had a lot of good chances," lamented Valencia boss Nuno Espirito Santo.
"We go away hurt, sad and angry because we wanted to win. In the first-half we had too many chances to end up with this result."
- Suarez stars again -Suarez scored two wonderful individual goals as Barca all but secured their place in the Champions League semifinals with a 3-1 win away to Paris Saint-Germain on Wednesday.
And he took less than a minute to pick up from where he left off in the French capital as Sergio Busquets fed Messi and his pass was fired low past Alves by Suarez for his 12th goal in as many games.
However, Valencia went on to dominate the remainder of the opening 45 minutes and were desperately unlucky still to be behind at the break.
Rodrigo flashed a shot just wide before he was deemed to have been brought down inside the area by Gerard Pique.
Parejo's penalty was poorly struck, though, and Bravo made a comfortable save low to his right.
Paco Alcacer then had a hat-trick of chances to grab a deserved equaliser as he turned Andre Gomes's dangerous cross wide, saw a goalbound effort blocked by Pique and struck the outside of the post.
Bravo was needed to come to his side's rescue again 15 minutes from time when he turned the ball behind from Rodrigo's volley.
But it was Messi who had the final word as he was given all the space he needed to break clear and score his 400th goal in 471 games for Barca in stoppage time as Valencia chased in vain for an equaliser.
A fourth consecutive La Liga win ensured Madrid remain in the title hunt, but victory could come at a cost with both Bale and Modric now fitness doubts for the decisive second-leg against Atletico on Wednesday with the tie locked at 0-0.
Bale was forced off with a left calf problem after less than five minutes with Javier Hernandez taking over in attack.
Carlos Kameni prevented the Mexican from opening the scoring with a fine save, but there was nothing he could do to prevent Ramos turning home Ronaldo's free-kick after 24 minutes.
Kameni produced more heroics to prevent Rodriguez doubling Madrid's advantage with a sweetly struck shot, but Malaga should have gone in level at the break as Sergi Darder slashed wide with the goal at his mercy.
Nordin Amrabat flashed wide with another good opening for the visitors after the restart before Madrid were dealt another injury blow as Modric hobbled off with a knee injury.
Madrid's bad luck continued as Ronaldo struck the post from the penalty spot after Rodriguez had been upended by Samu Castillejo.
However, there was no stopping Rodriguez's 14th goal of the season as he blasted into the top corner after a neat one-two with Ronaldo.
Malaga replied almost immediately as Juanmi headed home Roberto Rosales's cross, but Madrid saw out a nervous spell before Ronaldo slotted home from Hernandez's pass in stoppage time.
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