Alexis Sanchez gave Barca the lead before Dani Parejo swept home and Pablo Piatti headed in for the visitors.
Vibrant Valencia
Valencia are the first side to score three goals in a competitive game against Gerardo Martino's Barcelona
Lionel Messi made it 2-2 from the penalty spot after Ricardo Costa had handled, but Valencia grabbed a famous win when Paco Alcacer slotted in.
The La Liga champions were also reduced to 10 men when Jordi Alba was sent off.
The former Valencia player was dismissed for a body-check on Sofiane Feghouli 13 minutes from time.
Defeat was Barcelona's first at home in the league since a 2-1 loss to Real Madrid in April 2012.
"I would say to them [the Barcelona players that everything continues, that we may lose the leadership of the league, but that we will still continue to fight," said Barcelona manager Gerardo Martino.
"We will try to recover the lost ground on our title rivals. We conceded chances to Valencia and they took advantage of them. We need to keep going and keep in mind how much this hurt us today."
Barcelona remain top of the table on goal difference with 54 points, from Atletico Madrid, who play Real Sociedad on Sunday at 1800 GMT.
Real Madrid, who have won their last five league matches, are a point behind and are at Athletic Bilbao on Sunday (2000 GMT).
LINEUP, BOOKINGS (7) & SUBSTITUTIONS (5)
Barcelona
01 Valdés
22 Dani Alves
18 Alba Dismissed after an earlier booking
16 Busquets Booked
03 Piqué
14 Mascherano Booked
06 Xavi (Iniesta - 65' )
04 Fábregas (Tello - 77' )
10 Messi
09 Sánchez
07 Pedro
Substitutes
08 Iniesta
13 Pinto Colorado
15 Bartra
17 Song
20 Tello
21 Adriano
24 Sergi
Valencia CF
01 Alves Carreira Booked
19 Barragán
14 Bernat
15 Fuego Martínez
20 Moreira da Costa Booked
22 Mathieu
08 Feghouli
06 Romeu
16 Alcácer García (Vargas - 73' )
21 Parejo Booked (Herrero Javaloyas - 93' )
02 Piatti (Nicolás Cartabia - 87' )
Substitutes
03 Vezo
07 Gonçalves Oliveira
13 Guaita
17 Vargas
24 Herrero Javaloyas
28 Nicolás Cartabia
30 Portugués Manzanera
Ref: Pedro Jesús Pérez Montero
Att: 66,969
MATCH STATS
Possession
35%
65%
90mins
Barcelona
Valencia CF
Shots
208
On target
54
Corners
95
Fouls
188
Live Text Commentary
Full time
Full Time
Match ends, Barcelona 2, Valencia CF 3. 90:00 +4:00 Full time
Full Time
Second Half ends, Barcelona 2, Valencia CF 3. 90:00 +3:59 Booking
Booking
Sergio Busquets (Barcelona) is shown the yellow card. 90:00 +3:08 Booking
Booking
Diego Alves (Valencia CF) is shown the yellow card. 90:00 +2:12 Substitution
Substitution
Substitution, Valencia CF. Míchel replaces Daniel Parejo. 90:00 +1:17 Attempt missed. Lionel Messi (Barcelona) right footed shot from the centre of the box is close, but misses to the left. Assisted by Andrés Iniesta. 89:36 Attempt blocked. Lionel Messi (Barcelona) left footed shot from outside the box is blocked. Assisted by Dani Alves. 88:16 Foul by Javier Mascherano (Barcelona). 88:16 Daniel Parejo (Valencia CF) wins a free kick on the right wing. 87:21 Foul by Dani Alves (Barcelona). 87:21 Javi Fuego (Valencia CF) wins a free kick in the defensive half. 86:33 Substitution
Substitution
Substitution, Valencia CF. Fede replaces Pablo Piatti. 84:24 Corner, Valencia CF. Conceded by Andrés Iniesta. 83:46 Corner, Valencia CF. Conceded by Javier Mascherano. 83:18 Foul by Alexis Sánchez (Barcelona). 83:18 Jeremy Mathieu (Valencia CF) wins a free kick in the defensive half. 80:48 Attempt missed. Dani Alves (Barcelona) right footed shot from outside the box is close, but misses to the left. Assisted by Lionel Messi. 79:43 Attempt missed. Sofiane Feghouli (Valencia CF) right footed shot from outside the box misses to the left. Assisted by Javi Fuego following a corner. 79:06 Corner, Valencia CF. Conceded by Gerard Piqué. 78:24 Booking
Booking
Javier Mascherano (Barcelona) is shown the yellow card for hand ball.
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