Cu x Zn y S has p-type conductivity for a wide range of Cu content and a wide band gap (>3eV) with Zn-rich composition. In this work, Cu x Zn y S films were deposited by the photochemical deposition, where the film was deposited on the substrate immersed in the solution owing to reactions activated by UV light. The deposition solution contained 5mM CuSO 4 , 25mM ZnSO 4 and 400mM Na 2 S 2 O 3 . The deposited film showed transmission larger than 70% in the visible range, and its band gap was about 3.7eV. pn heterostructures were fabricated by depositing ZnO on the Cu x Zn y S film by the pulse-biased electrochemical deposition from a solution containing 100mM Zn(NO 3 ) 2 . When the ZnO film thickness was larger than 1μm, the heterostructures showed rectification properties and weak photovoltaic effects.