To explore the diversity of structure and optoelectronic applications of metal chalcogenide cluster materials, two Sb-based chalcogenide cluster compounds [Sb₄S₅(S₃)]·C₅H₁₁N (1) and (C₅H₁₂N)₂[In₂Sb₂S₇] (2) have been synthesized through solvothermal method using asymmetric coordination geometry with Sb(Ⅲ) containing lone pair electrons and sulfur. The two compounds consist of combinations between {SbS₃} or {InS₄} coordination units in a vertex-sharing manner, respectively. The electrocatalytic oxygen reduction reaction (ORR) studies showed that the limit current density and half-wave potential of compound 2 were higher than those of compound 1, indicating better ORR performance. The Koutecky-Levich plot analysis showed that the ORR catalytic process of layered compound 2 constructed from mixed metals is mainly through a four-electron pathway.