Di-and triorganotin(IV) derivatives of tyrosylalanine (H 2 Tyr-Ala) with general formula R 2 Sn(Tyr-Ala) (where R = Me, n-Bu, nOct, and Ph) and R 3 Sn(HTyr-Ala) (where R = Me and Ph) have been synthesized and structurally characterized in the solid state as well as in solution on the basis of various spectroscopic techniques, namely. FT-IR, multinuclear ( 1 H, 13 C and 119 Sn) NMR and 119 Sn Mössbauer. These investigations suggest that tyrosylalanine in R 2 Sn(Tyr-Ala) acts as dianionic tridentate ligand coordinating through carboxylate oxygen [-C(O)O − ], amino (-NH 2 ), and (CO)N − peptide nitrogen, while in the case of R 3 Sn(HTyr-Ala), the ligand acts as monoanionic bidentate coordinating through -C(O)O − and -NH 2 , and the polyhedron around tin in R 2 Sn(TyrAla) and R 3 Sn(HTyr-Ala) is a distorted trigonal-bipyramidal. Equilibrium (pH-metric) studies of the interaction of Me 2 Sn(IV) 2+ and Me 3 Sn(IV) + with dipeptides namely, tyrosylalanine (H 2 Tyr-Ala), glycyltyrosine (H 2 Gly-Tyr), and glycylisoleucine (H 2 Gly-Ile), in aqueous solution (I = 0.1 M KNO 3 , 298 K) have also been carried out. The concentration distribution of the various complex species in solution has been evaluated as a function of pH. It has been found that in these dipeptides, [-C(O)O − , N − , NH 2 ] coordinated complexes are dominant in the neutral pH range with a trigonal-bipyramidal structure. The complex species formed are water soluble in the pH range 2.7-10.5. In all of the studied systems, no polymeric species have been detected in the experimental pH range. Beyond pH 8.0, significant amounts of hydroxo species, namely. Me 3 Sn(OH) and Me 2 Sn(OH) 2 , are formed.