Organotin complexes 1–6 of the general formula [SnR2L] and [(SnR3)2L] (L=phenanthrenequinone dioximato – a bidentate ligand, R=Me, Bu, and Ph) were synthesized by the reaction of the sodium salt of the ligand H2L (prepared in situ with MeONa) and SnR2Cl2/SnR3Cl in 1 : 1 and 1 : 2 molar ratios. The physical and spectral properties of the newly synthesized complexes 1–6 are described. DFT and HF Calculations were performed to confirm the proposed structures.