The central copper(II) atom of the title salt, {[Cu(CF3SO3)(CH3CN)2(C12H12N2O2)](CF3SO3)}
n
or [[Cu(CH3CN)2(diOMe-bpy)(CF3SO3)](CF3SO3)]
n
where diOMe-bpy is 4,4′-dimethoxy-2,2′-bipyridine, C12H12N2O2, is sixfold coordinated by the N atoms of the chelating bipyridine ligand, the N atoms of two acetonitrile molecules, and two trifluoromethanesulfonate O atoms in a tetragonally distorted octahedral shape. The formation of polymeric chains [Cu(CH3CN)2(diOMe-bpy)(CF3SO3)]+
n
leaves voids for the non-coordinating trifluoromethanesulfonate anions that interact with the complex through weak hydrogen bonds. The presence of weakly coordinating ligands like acetonitrile and trifluoromethanesulfonate makes the title compound a convenient starting material for the synthesis of novel metal–organic frameworks.