CdS thin films have been deposited onto FTO/glass substrates by two different techniques, electrochemical deposition (ECD) and chemical bath deposition (CBD). Feasibility of using these two film types in photoelectrochemical processes has been critically investigated here. The films were comparatively characterized by a number of techniques (solid state absorption spectra, solid state photoluminescence spectra, XRD and SEM). PEC characteristics of the electrodes, including current density–voltage (J–V) plots, conversion efficiency (η), stability and fill-factor (FF) were then studied. The results show that both systems involved nano-sized CdS particles living in coagulates. The ECD was thinner and more uniform than the CBD system. The CBD films were more effective in PEC processes than the ECD counterparts. Effect of annealing on characteristics of both electrode systems has been investigated. Annealing enhanced both film characteristics, but the CBD was affected to a higher extent, and the annealed CBD film was more effective than the ECD counterpart.