Four novel diorganotin(IV) complexes with general formula R2SnL (R= nBu, PhCH2) were synthesized from diorganotin dichlorides and binary Schiff‐bases (H2L) containing N2O2donor atoms in the presence of sodium ethoxide. The Schiff bases were prepared by reactions of o‐phenylenediamine with 3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzaldehyde (H2L1) and salicylaldehyde (H2L2) respectively. The compounds were characterized by elemental analyses, IR, and NMR spectroscopy. The solid‐state crystal structure of the compound nBu2SnL1was determined by single‐crystal structural analysis.