Photoactive　Cu(I)　complexes　are　promising　luminescent　materials　owing　to　their　abundant　reserves　and　marvelous　biocompatibility.　In　this　work,　we　report　the　synthesis　and　characterization　of　two　binuclear　sulfur‐bridged　Cu(I)　complexes　(POP)2Cu2(μ‐HS/Cl)2 ⋅ 0.92MeOH　1　(POP=(oxybis(2,1‐phenylene))bis(diphenylphosphine))　and　(POP)2Cu2(μ‐HS)2　2,　which　were　prepared　by　one‐pot　facile　solvothermal　method　with　copper‐4‐tert‐butylbenzenethiol　(CuSC6H4tBu)　and　POP　as　precursors.　Complex　1　exhibits　sky‐blue　emission　while　complex　2　displays　blue.　Complex　1　was　systemically　investigated　by　PXRD,　UV‐vis　spectrum,　IR,　TGA　and　steady‐state　spectra.　Temperature‐dependent　steady‐state　emission　and　decay　lifetime　indicate　that　complex　1　is　a　typical　phosphorescent　emitter.