The effect of annealing of the n-Si semiconductor on its characteristics in photoelectrochemical systems has been investigated. The annealing improved the dark current density vs. potential plots. The surface was improved by annealing, as manifested by SEM results. The effect of the cooling rate on preheated n-Si wafers was also investigated. It was found that the slowly cooled electrodes gave better dark current density vs. potential plots,for samples annealed at lower than 550°C. For samples annealed at higher temperatures, quenching gave better dark-current density vs. potential plots. SEM measurements showed parallel results to these findings. Enhanced surface textures were observed for slowly cooled wafers from temperatures below 550°C. Samples quenched from temperatures above 550°C showed better surfaces than slowly cooled counterparts.