Charge-transfer (CT)-photolysis of Cu(II) dithiocarbamate mixed-ligand complexes Cu(II)(Et 2dtc)X (X=Cl −, Br −) and Cu(II)(Et 2dtc) +⋯Y − (Y=ClO 4 −, NO 3 −) has been studied in toluene/ROH and compared with our previous data obtained in chloromethane/ROH solutions, where chloromethane=CCl 4, CHCl 3 or CH 2Cl 2 and ROH=MeOH, EtOH, i-PrOH or i-BuOH. An EPR evidence is obtained about the formation of a new copper(II) dithiocarbamate mixed-ligand complex during simultaneous photolyses of Cu(II)(Et 2dtc) + and Cu(II)(Et 2dtc) 2 species in toluene/ROH. The role of the solvent is discussed from the combined analysis of spectrophotometric and EPR data and quantum yield results.