Three cis‐bis{5‐[(E)‐2‐(2‐carbomethoxyphenyl)‐1‐diazenyl]quinolinolato}‐diorganotin(IV), R2Sn(L)2, complexes [R = Me (1), Ph (2) and Bz (3)] were synthesized and characterizedby 1H‐, 13C‐, 119Sn‐ NMR, IR, and 119Sn Mössbauer spectroscopic techniques in combination with elemental analysis. The structure of diphenyltin(IV) complex Ph2Sn(L)2 (2) was determined by single‐crystal X‐ray crystallography as its tri‐benzene solvate. Each complex was found to adopt a distorted cis‐R2 octahedral arrangement around the tin atom with the quinolinolato ligands being N,O‐chelating; the oxygen atoms are trans to each other. The complexes retain their solid‐state structure in non‐coordinating solvents as evidenced by119Sn‐NMR spectroscopy.