Metal chalcogenides are a special class of semiconducting materials characterized by their rich structures and compositions, making them a promising option for a broad range of applications in the field of inorganic chemistry. However, the path forward is not without its challenges, notably in the realms of interface management and enhancing carrier concentration. To address these issues, we solvothermally synthesized two novel chalcogenidoantimonates [Zn(tren)]2Sb2Se5 (1) [tren = tris (2-aminoethyl) amine] and [Zn(tepa)H]2Sb2S6 (2) (tepa = tetraethylenepentamine) utilizing transition metal Zn by band gap optimization strategy in the visible region. Both compounds exhibited distinct zero-dimensional cluster structures, with transition metal complex cations acting as structure-directing agents. A comprehensive analysis of the electronic structure, band gap, and photocurrent response of these crystals was undertaken, revealing significantly enhanced photocatalytic properties compared to preceding studies. This research underscores the potential of antimony chalcogenides in the realm of photoelectric properties and promotes the applications of chalcogenides.