Biphenyl-4-thiol (B4t) functionalised p-GaAs photocathodes were compared to non-functionalised p-GaAs ones in the presence of methyl viologen cation radical (MV+•) as a redox mediator. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) studies revealed that at bare p-GaAs photocathodes the radical interacts strongly with the electrode surface, displaying unwanted surface states (SS) mediated electron transfer (ET) even in the dark. Functionalising the electrode with B4t passivated the interface against this unwanted process, while ensuring that the conduction band (CB) electrons still facilitated faradaic reduction of MV+• to MV0 with unhindered efficiency.