A series of easily accessible linear N-heterocyclic carbene (NHC) copper(I) complexes, bearing pyridine (py) and its derivatives as chromophore ligands, are barely emissive in the single-crystalline solid state. However, their powders, neat films, and dilute doped films of poly(methyl methacrylate) (PMMA; 1-10%) show very intense blue-to-blue-green photoluminescence with remarkable quantum yields phi of up to 87% and microsecond lifetimes, indicative of triplet states being involved. These luminescence properties are similar to trigonal coordinated NHC copper(I) bis(pyridine) complexes, which we have also isolated and characterized with respect to their structures and photophysics. provide detailed insight into the nature of the luminescence enhancing effect Our spectroscopic and theoretical studies of the linear two-coordinated copper(I) compounds, which is based on the formation of Cu-F interactions between the BF4- anions and [Cu(NHC)(2-R-py)](+) (R = H, Me, Ph) cations. These interactions are absent in the single crystals but lead to a distorted ground-state structure in the precipitated powders or in PMMA films, giving rise to high k(r). In addition, we found that our linear copper(I) complexes exhibit mechanochromic luminescence because grinding of the single crystals leads to enhanced emission intensity. In light of the recently reported cation-anion contact-induced mechanochromic luminescence of two-coordinated copper(I) complexes, this study supports the generality of this new mechanism for the design of mechanoresponsive phosphorescent materials.