Various carbon materials were used as support of polyvinylpyrrolidone (PVP)-capped Pd nanoparticles for the synthesis of catalysts for the production of hydrogen from formic acid dehydrogenation reaction. Among investigated, MWCNT-supported catalysts were the most promising, with a TOF of 1430 h −1 at 80 • C. The presence of PVP was shown to play a positive role by increasing the hydrophilicity of the materials and enhancing the interface contact between the reactant molecules and the catalytic active sites.