Cu2ZnSnS4 (CZTS) nanocrystals (NCs) were prepared via a one-pot solvothermal method. Given that the composition affects the electronic properties of this p-type semiconductor, two compositional ratios were chosen from 10 designed and synthesized analogues, one yielding Cu-poor and the other Custoichiometric CZTS. NCs in which the Cu concentration was slightly below stoichiometric yielded more uniform films with greater photovoltaic performance. The lower Cu content also lead to slightly better crystallinity within the film, as demonstrated by XRD, Raman spectroscopy and transmission electron microscopy. Chronophotoelectrochemical measurements indicated that both types of NC films displayed good stability; however, with a decrease in potential, an increase in resistance for the Cu-stoichiometric film was observed. As determined by intensity modulated photocurrent spectroscopy, the product separation rate of the photoinduced holes and electrons in the Cu-poor films were more than 3 times that of the Cu-stoichiometric, confirming that the lower Cu content led to an improved photoperformance. (C) 2015 Elsevier Ltd. All rights reserved.