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Two ionic triphenyltin(IV) chloride carboxylate compounds of the formula [NHEt3][Ph3SnCl(L)] [LH = N‐phthaloylglycine (P‐GlyH), 1; 1,2,4‐benzenetricarboxylic 1,2‐anhydride (BTCH), 2] were tested for the in vitro activity against 518A2 (melanoma), FaDu (head and neck carcinoma), HT‐29 (colon cancer), MCF‐7 (breast carcinoma), and SW1736 (thyroid cancer) cell lines. The ammonium salts of the carboxylic acids are found to be not active, while anionic [Ph3SnCl(L)]− exhibited high cytotoxicity in nM range, both higher activity and selectivity than cisplatin. Compounds 1 and 2 are inducing apoptosis, which was proved with the morphological and biochemical features such as membrane blebbing, translocation of phosphatidylserine, and DNA fragmentation. Thus, accumulation of cells in sub‐G1 phase is observed. Both anionic organotin(IV) compounds showed potent cytotoxic and apoptotic properties against five cancer cell lines of various histogenetic origin.