Cu1−δZn2−xSnxS4 (CZTS) films were prepared by sequential electrochemical deposition on different supports (Ta, Ti, Mo, and glass—Mo). The samples obtained using preliminary annealing in inert nitrogen atmosphere contained a secondary intermetallic phase Cu6Sn5 that did not disappear upon subsequent annealing in reactive sulfur atmosphere at 550 °C for 30 min. The CZTS films prepared without preliminary annealing in inert nitrogen atmosphere contained a minimum amount of secondary phases after the sulfurization step. The samples prepared were characterized by a photovoltaically suitable band gap of 1.5 eV and p-type conductivity.