In this report for the first time the effect of different metal hexacyanoferrate (MHCF) films on hydrogen evolution reaction (HER) was studied. Some single and mixed MHCFs including CoHCF, CuHCF, NiHCF, PbHCF, Ba–NiHCF, Co–NiHCF, Co–PbHCF, Co–CuHCF, Cu–NiHCF, Cu–PbHCF, Mn–NiHCF, Ni–PbHCF and Ni–ZnHCF were simply electrodeposited on carbon paste electrode (CPE) and their performance for HER were examined in acidic, neutral and alkaline media. Presence of these mediators caused to improvement of hydrogen generation on CPE. Among these mediators Ni–PbHCF had the best efficiency with the lowest over potential for hydrogen evolution in 2M H2SO4. Also, applying several successive potential cycles for HER on the electrode modified with Ni–PbHCF did not reduce the performance of the electrode for hydrogen generation.