Reaction of the potassium salts of N-thiophosphorylated thioureas RNHC(S)NHP(S)(OiPr)2 (R = Me, HLII; 2-MeC6H4, HLIIII; and 6-MePy-2, HLIII) with CuI in aqueous EtOH leads to the polynuclear complexes [CuLI]n (1), [Cu3LII3] (2) and [Cu4LIII4] (3). Reaction of the potassium salts KLII–III–III–III with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to the binuclear [Cu2(Ph2PCH2PPh2)LII2] (4) and [Cu2(Ph2PCH2PPh2)LIII2] (5), or mononuclear [Cu(PPh3)2LII,III] (6 and 7), [Cu{Ph2P(CH2)2PPh2}LII,III] (8 and 9), [Cu{Ph2P(CH2)3PPh2}LII,III] (10 and 11), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI–III] (12–14) complexes. The structures of these compounds were investigated by elemental analysis, 1H, 31P{1H} NMR and UV-Vis spectroscopy. The crystal structures of HLIII, 2, 3, 6 and 12 were determined by single-crystal X-ray diffraction. The luminescent properties of the complexes in the solid state are reported.