Treatment of bis(diphenylphosphino)methane (dppm) and 2-(diphenylphosphanyl)pyridine (dpppy) with Cu(CH₃CN)₄BF₄ afforded a dinuclear Cu(I) complex [Cu₂(dpppy)₂(dppm)(CH₃CN)](BF₄)₂·3CH₂Cl₂ (1). Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail. It crystallizes in triclinic space group P with a = 13.0834(8), b = 13.5568(8), c = 21.8544(11) Å, α = 76.090(5)°, β = 80.803(5)°, γ = 64.582(6)°, V = 3391.3(3) ų, Z = 2, M_r = 1507.42, D_c = 1.476 g/cm³, F(000) = 1532, GOOF = 1.071, the final R = 0.0700 for 9041 observed reflections with I > 2σ(I) and wR = 0.2063 for all data. The complex contains a Cu₂-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement. In the crystalline phase, complex 1 exhibits bright bluish-green photoluminescence (λ_max = 488 nm) with high quantum yield (ϕ = 0.57) at room temperature. It is still a relatively high emission quantum yield (ϕ = 0.36) in doped PMMA thin film with 20 wt% dopant of complex 1. The emission peaks of 1 in dichloromethane solution and doped PMMA (20 wt%) thin films are 510 and 494 nm, respectively, showing a very slight bathochromic shift compared to that in crystalline phase. This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper centers in the excited state.