Abstract The photoelectrochemical (PEC) properties of sputtered aluminum doped hydrogenated amorphous silicon carbide thin films grown on p-type crystalline silicon substrates were investigated in 1 M H 2 S O 4 solution under chopped light illumination. Optical and structural properties of the top absorber layer were systematically assessed after post-deposition isochronical annealing treatments. Samples exhibited a noticeable improvement of the opto-electronic properties after thermal treatments. In addition, an abrupt enhancement of the photocurrent was observed reaching a saturation value of 17 mA cm⁻² at −1.75 V vs. Ag/AgCl (3.5 M KCl). In this research we propose that this enhancement effect is associated to a charge transfer kinetic mechanism influenced by surface states and the p-type substrate. The latter most likely due to the space charge region extending beyond the absorber layer reaching the substrate. Current density-potential and electrochemical impedance spectroscopy measurements in dark revealed a reduction of the S i O 2 native layer at cathodic potentials higher than −1 V vs. Ag/AgCl (3.5 M KCl), which contributes to the high charge transfer kinetic of the system. We believe that these results will contribute to understand the substrate influence in the PEC performance of top absorber layers in multilayer structures for solar water splitting.