In recent decades, chalcogenides have appealed extensive attention due to potential applications in photoelectric materials. Two selenidostannates, [Fe1.11Zn0.89(en)3]2Sn2Se6 (1, en = ethylenediamine) and [Co1.24Zn0.76(en)3]2Sn2Se6 (2) were synthesized by solvothermal method with ethylenediamine and ethylene glycol as the solvents, both consisting of complexes in which the two different transition metals occupied the same position and [Sn2Se6]4− anions. Transition metal complexes (TMCs) can combine photoelectric properties with inorganic skeletons to extend their compound properties. Therefore, we investigated the photocurrent response of both compounds and found higher transient photocurrent densities. The band gaps of compounds 1 and 2 were calculated to be 2.31 eV and 2.17 eV, respectively, indicating that two compounds have potential semiconductor properties. In addition, we also studied the photodegradation efficiency of compounds 1 and 2 and found that the degradation efficiency of two compounds could be achieved 84.5 % and 55.9 %, which indicated that the compounds have excellent photocatalytic properties. The field of photoelectrocatalytic research on selenidostannates is broadened.