Both a persulfide crystal of L-L(1), the oxidative coupling product of 1-phenyl-1H-tetrazole-5-thiol(HL), and a neutral copper(I) complex of Cu6L6(2) were self-assembled and their crystal architectures were characterized by CCD method. HL was converted into the persulfide L-L(1) over a metalloporphyrin catalyst with enzymatic characters under ambient conditions. Whlie in the crystal architecture of Cu6L6(2), 6 copper(I) ions were ligated by 6L-anions to construct a Cu6 ring, which just resembled the chair configuration of cyclohexane. Notably, both compounds 1 and 2 exhibit strong photoluminescence in solid state. Both of a persulfide crystal of LL (1), the oxidative coupling product of 1-phenyl-1H-tetrazole-5-thiol (HL), and a neutral copper (I) complex of Cu6L6 architectures were characterized by CCD method. HL was converted into the persulfide LL (1) over a metalloporphyrin catalyst with enzymatic characters under ambient conditions. Whlie in the crystal architecture of Cu6L6 (2), 6 copper (I) ions were ligated by 6L- anions to construct a Cu6 ring, which just resembled the chair configuration of cyclohexane. Notably, both compounds 1 and 2 exhibit strong photoluminescence in solid state.