Cu2ZnSnS4 (CZTS) films grown on transparent conducting electrodes using a sol–gel method were pre-examined for future bifacial and tandem solar cell applications. Thin film containing Cu–Zn–Sn was prepared by solution based precursor on a SnO2-F/(FTO) coated glass substrate, which was subsequently annealed in a sulfur environment to obtain a CZTS phase. The photocurrent response of CZTS film was measured using alternating front illumination and rear illumination in a Eu3+/Eu2+ solution environment. The photoelectrochemical response exhibited during rear illumination is comparable to that obtained for front illumination. The promising photocurrent data for CZTS films suggest these films have potential application in semitransparent photovoltaic devices.