The synthesis, characterization, and emission properties of 2-coordinate dicopper(i) complexes bearing two trimethylene-bridged bis-NHC ligands, [Cu2(L3Me)2](PF6)2 (1), [Cu2(L3Et)2](PF6)2 (2), [Cu2(L3Bu)2](PF6)2 (3), [Cu2(L3MeOPh)2](PF6)2 (4) and [Cu2(L3Mes)2](PF6)2 (5), where L3R denotes trimethylene-bridged bis(N-heterocyclic)carbene (NHC) ligand substituted by two R groups at the nitrogen atoms of NHC, have been investigated. The quantum yield, Φ, and the lifetime, τ, of the emission of 2, are 0.21 and 25 μs, respectively in methanol, which is a well-known solvent for quenching the luminescence of many copper(i) complexes. The 8-shaped geometry of the dicopper(i) complexes brings a considerable copper(i)-copper(i) interaction which affects the luminescent properties. Additionally, we find that methoxyphenyl and mesityl groups substituted at the nitrogen atom of the NHC moiety drastically stabilize the bis(NHC) copper(i) complexes even in air-saturated acetone-d6.