In this paper, we reported syntheses of 6 compounds of a series of dibutyltin(IV) and diphenyltin(IV) dihydroxybenzoate compounds which have successfully been prepared from the starting materials of dibutyltin(IV) dichloride and diphenyltin(IV) dichloride respectively via the intermediate products of dibutyltin(IV) oxide and diphenyltin(IV) dihydroxide with o-, m-, and p-hydroxybenzoic acids. The new compounds synthesized were well characterized by 1H and 13C NMR, IR and UV-Vis spectroscopies as well as based on the microanalytical data. The anticorrosion activities of these compounds were tested toward HRP mild steel in NaCl medium using potentiodynamic methods. The results indicated that the diphenyltin(IV) compounds showed much better activity than those of dibutyltin(IV) analogous. The results obtained indicated that the higher anticorrosion activities were observed to depend on the nature of the ligand attached to the Sn centre. The number of carbon atoms present in the ligands attached to the metal center might also play an important role.