In an attempt to obtain molecular H2 production electrocatalysts achieving balanced basicity and reduction potential, we focused on the mono-substituted diiron-dithiolate derivative [Fe2(µ-bdt)(CO)5(P(OMe)3)] (bdt = benzenedithiolate). The electrocatalytic efficiency of this iron-iron hydrogenase model was determined by cyclic voltammetry in acetonitrile using p-toluenesulfonic acid as a proton source. Detailed analysis of the current – potential responses and comparison with the all-CO diiron-dithiolate parent compound clearly show that the effect of the chemical properties on the electrocatalytic efficiency is not fully determined by the turnover frequency under pseudo-first-order approximation and the overpotential defined as the difference between the reduction potential of the electrocatalysts in the absence of acid and the reversible potential of the couple H2/acid.