The synthesis and photophysical study of two dinuclear copper(I) complexes bearing a 2-(1H-imidazol-2-yl)pyrimidine bridging ligand are described. The tetrahedral coordination sphere of each copper center is completed through the use of a bulky bis(phosphine) ligand, either DPEphos or Xantphos. Temperature-dependent photophysical studies demonstrated emission through a combination of phosphorescence and thermally activated delayed fluorescence for both complexes, and an intense emission (Phi(PL) = 46%) was observed for a crystalline sample of one of the complexes reported. The photophysics of these two complexes is very sensitive to the environment. Two pseudopolymorphs of one of the dinuclear complexes were isolated, with distinct photophysics. The emission color of the crystals can be changed by grinding, and the differences in their photophysics before and after grinding are discussed.