In this work, a new Cu(I) complex ［CuBr(L)(PPh3)2］·2CH3OH (1) was synthesized using triphenylphosphine (PPh3) and 5-methoxybenzimidazole-2-thiol (L). The complex was characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetric analysis and other various spectroscopic analyses. X-ray crystallographic analysis reveals that complex (1) crystallizes in the monoclinic system with P21/c space group. Each central metal ion is four-coordinated with one bromide ion, two phosphorus atoms from two PPh3 ligands and one sulphur atom from one L ligand, resulting in a mononuclear complex. In addition, the fluorescence spectra of 1 in methanol solution and solid state show that the emission mechanism belongs to metal-to-ligand charge transfer (MLCT) based on PPh3. The difference of the fluorescence emission maximum of 1 in the methanol solution is not shifted compared to PPh3, while red-shifted by 6 nm compared to PPh3 in solid state, indicating that the structure of 1 in methanol solution is different from that in solid state.