Cationic and neutral mononuclear Cu(I) complexes, [Cu(PPh 3 ) 2 (PmH)]BF 4 (1a), [Cu(DPEphos) (PmH)]BF 4 (2a), [Cu(Xantphos) (PmH)]BF 4 (3a), [Cu(PPh 3 ) 2 (Pm)] (1b), [Cu(DPEphos) (Pm)] (2b) and [Cu(Xantphos) (Pm)] (3b) (PPh 3 = triphenylphosphine, DPEphos = bis(2-diphenylphosphinophenyl)ether, Xantphos = 9, 9-dimethyl-bis(diphenylphosphino)xanthenes, PmH = 2-(pyridin-2-yl)benzimidazole, Pm=(2-(Pyridin-2-yl)benzimidazolate), have been prepared and characterized by IR, 1 H NMR, 13 C NMR, 31 P NMR, XRD, elemental analysis and X-ray crystal structure analysis. The structural analysis shows that each of Cu(I) complexes includes a tetrahedral [Cu(NN) (PP)] + moiety, and temperature variation from 99 K to 298 K leads to the change of bonds lengths, angles and weak interactions. Meanwhile, theoretical calculations indicate that the differences between cationic and neutral Cu(I) complexes affect the composition of HOMO and LUMO orbitals, and the effect of temperature on Mülliken atomic charges is limited. Furthermore, neutral Cu(I) complexes 1b–3b show better luminescence in comparison to cationic Cu(I) complexes 1a-3a at room temperature, and temperature variations from 99 K to 298 K result in changing photoluminescence to some extent, which partly agrees with the related calculation results. In these cationic and neutral Cu(I) complexes, the maximum phosphorescent lifetime and quantum yield reach respectively 137 μs and 42% at room temperature. Moreover, cationic and neutral Cu(I) complexes are utilized to fabricate the monochromatic LEDs, showing favorable electroluminescence with the maximum EQE of 7.10%. Crystal structures, theoretical calculation and luminescent properties of cationic/neutral mononuclear Cu(I) complexes are investigated at room temperature and different temperatures, and then these Cu(I) complexes are applied to light-emitting diodes. • Crystal structures, electronic and luminescent properties of cationic/neutral Cu(I) complexes are investigated. • In these Cu(I) complexes, the maximum room-temperature phosphorescent lifetime and quantum yield reach 137 μs and 42%, respectively. • All Cu(I) complexes are used for fabricating monochromatic LED devices, showing favorable electroluminescence.