The influence of the elemental composition of CuZnSn coatings deposited by electrodeposition on the formation of the Cu 2 ZnSnSe 4 crystal structure following a selenisation process was investigated using X-ray diffraction, scanning electron microscopy and Raman spectroscopy. This study showed that the optimum alloy ratio to achieve the Cu 2 ZnSnSe 4 crystal without impurity phases was in the range of 0.37–0.50 for Cu/(Zn+Sn) and 2.5–4 for Zn/Sn.