The first paradigm of halide-controlled interconversion between two- and three-coordinate copper(I) complexes, [Cu(LPh)](ClO4) (1·ClO4) and [Cu(LPh)I] (2), where LPh = 1,3-bis-(3,5-dimethyl-pyrazol-1-ylmethyl)-2-phenyl-2,3-dihydro-1H-perimidine, was presented, which can result in reversible fluorescence changes.