Hydrogen production by splitting water using electrocatalysts powered by renewable energy from solar or wind plants is one promising alternative to produce a carbon-free and sustainable fuel. Earth-abundant and nonprecious metals are, here, of interest as a replacement for scarce and expensive platinum group catalysts. Ni–Mo is a promising alternative to Pt, but the type of the substrate could ultimately affect both the initial growth conditions and the final charge transfer in the system as a whole with resistive junctions formed in the heterojunction interface. In this study, we investigated the effect of different substrates on the hydrogen evolution reaction (HER) of Ni–Mo electrocatalysts. Ni–Mo catalysts (30 atom % Ni, 70 atom % Mo) were sputtered on various substrates with different porosities and conductivities. There was no apparent morphological difference at the surface of the catalytic films sputtered on the different substrates, and the substrates were classified from microporous to flat. The electrochemical characterization was carried out with linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) in the frequency range 0.7 Hz–100 kHz. LSV measurements were carried out at direct current (DC) potentials between 200 and −400 mV vs the reversible hydrogen electrode (RHE) in 1 M NaOH encompassing the HER. The lowest overpotentials for HER were obtained for films on the nickel foam at all current densities (−157 mV vs RHE @ 10 mA cm^–2), and the overpotentials increased in the order of nickel foil, carbon cloth, fluorine-doped tin oxide, and indium tin oxide glass. EIS data were fitted with two equivalent circuit models and compared for different DC potentials and different substrate morphologies and conductivities. By critical evaluation of the data from the models, the influence of the substrates on the reaction kinetics was analyzed in the high- and low-frequency regions. In the high-frequency region, a strong substrate dependence was seen and interpreted with a Schottky-type barrier, which can be rationalized as being due to a potential barrier in the material heterojunctions or a resistive substrate–film oxide/hydroxide. The results highlight the importance of substrates, the total charge transfer properties in electrocatalysis, and the relevance of different circuit components in EIS and underpin the necessity to incorporate high-conductivity, chemically inert, and work-function-matched substrate–catalysts in the catalyst system.