The Catalans are keen to add some fresh blood to their defence following the departure of Carles Puyol and they have earmarked Mathieu as a useful replacement for the former Spain international.
Barca had been locked in talks with Valencia for a number of weeks over the 30-year-old, but both clubs reached an agreement at last on Monday over a deal worth close to €20 million [£15.8m].
Mathieu is expected to be confirmed as a new Barcelona player in the upcoming days, yet Marquez - who made 240 appearances for Barca - feels the Catalans would be better off turning their attentions elswhere.
"I don't think he has the profile to play for Barcelona and even less so for this price," Marquez said in an interview with RAC1.
"Hopefully they'll think well about this and if they're going to splash out like that, it's for someone who is actually worthwhile."
Mathieu started his professional career with Sochaux and also wore the Toulouse jersey before joining Valencia in the summer of 2009. He has made over 100 official appearances for the Liga outfit since.