A highly selective decomposition of formic acid in aqueous medium was achieved with immobilized catalysts. In the gas product of all of the experiments, only hydrogen and carbon dioxide were detected. The activity of different immobilized catalysts for the decomposition of formic acid was checked, and the highest turnover frequency (TOF) was observed using Pd-S-SiO2. Moreover, we have found that the addition of sulfates could significantly promote the activities of mercapto-functionalized catalysts by 30-70%, which is attractive for practical applications.