Kesterite Cu2ZnSnS4 (CZTS) thin films in which the Cu site was partially replaced with Ag were prepared by spray deposition on an Mo-coated glass substrate. Successful replacement of Cu components in the CZTS lattice with Ag up to an Ag/(Cu + Ag) ratio of 0.20 was achieved. Samples with relatively low contents of Ag (Ag/(Cu + Ag) ratios of 0.05 and 0.10) showed obvious grain growth compared to that of bare CZTS, whereas samples with higher Ag contents showed an appreciable decrease in grain sizes. Photoelectrochemical properties for water reduction (H2 production), which was examined after surface modifications with an In2S3/CdS double layer and Pt catalyst for H2 evolution, depended strongly on such morphological differences; a maximum conversion efficiency, i.e., half-cell solar to hydrogen efficiency, of 2.4% was achieved by the photocathode based on the film with an Ag/(Cu + Ag) ratio of 0.10. Minority carrier dynamics examined by photoluminescence measurements indicated that such an active sample of PEC H2 production had a relatively long carrier lifetime, suggesting that the suppression of carrier recombination at grain boundaries in the bulk of these kesterite films is one of the important factors for enhancing PEC functions.