The defender has signed an extended three-year contract to end speculation linking him with a Camp Nou switch this summer
The 29-year-old had just 12 months remaining on his pre-existing contract but he is now set to stay at the Mestalla until June 30, 2017.
The deal, revealed by Mathieu on Friday, means that he has snubbed interest from Tito Vilanova's side, but he claims that he wanted to show his current club loyalty instead of wait in the hope that the Liga champions chose to swoop this summer.
"I am very happy, it is all done, I have renewed for Valencia," the Frenchman told reporters after signing.
He told L'Equipe: "Barca were interested in me, but I came in fourth or fifth on their list. I could have waited, but I had to show respect towards Valencia."
The France international made the switch from left-back to centre-back for much of the season with los Che and impressed many with his versatility in defence.