Tris(2-pyridyl)phosphine oxide reacts with CuSCN to form a variety of luminescent complexes, depending on the specified metal-to-ligand ratio and the solvent used, viz. mononuclear [Cu(N,N′,N′′-Py₃PO)(NCS)], dinuclear (N,N′-Py₃PO)Cu(^SCN_NCS)Cu[(N,N′-Py₃PO)], their co-crystal (2 : 1, correspondingly) and trinuclear {Cu(NCS)[SCNCu(N,N′,N′′-Py₃PO)]₂}. In the solid state, these complexes feature red-orange emission upon UV photoexcitation. The reaction of tris(2-pyridyl)phosphine with CuSCN quantitatively produces an almost insoluble coordination polymer, [Cu(Py₃P)NCS]_n, which exhibits bright green emission. The synthesized compounds are the first members of the hitherto unknown family of Cu(I) thiocyanate complexes supported by tripodal ligands.