Cu 2ZnSn(SxSe1−x)4 (CZTSSe) layers deposited from multi-component nanoparticle inks were characterized by modulated surface photovoltage (SPV) spectroscopy to investigate the effect of annealing conditions. The SPV signals increased strongly with decreasing sulfur content. Band gaps were obtained in terms of SPV onset energy. A diffusion length of above 1 μm was estimated for photo- generated electrons at x = 0.28. The band gap increased with increasing x showing an anomaly in the range of 0.5 < x < 1. The results suggested that an excess of selenium is required for the formation of a photo-active phase reliable for efficient Cu 2ZnSn(SxSe1−x)4-based solar cells.