Eight new organotin(IV) carboxylates of general formula RnSnL4‐n have been synthesized by the reaction of respective organotin(IV) oxide/chloride with stoichiometric amount of the ligand, (E)‐2,3‐bis(4‐chlorophenyl)‐2‐propenoic acid or its silver salt in dry toluene using Dean and Stark apparatus accordingly. The synthesized carboxylates were characterized using multinuclear (1H, 13C, 119Sn) NMR, FT‐IR spectroscopies and mass spectrometry in combination with the elemental analysis and melting point determination. The data reveal that tri‐ and diorganotin(IV) carboxylates adopt penta‐ and hexa‐coordination around tin moiety in solid states, respectively. All compounds were preliminary screened for antimicrobial, antifungal, and cytotoxicity studies, and some of the compounds exhibit promising results.