A series of Sn(II) and Sn(IV) compounds containing ketiminate ligands were synthesized. Reactions of SnCl 2 with 1 or 2equiv. Li[OCMeCHCMeNAr] (where Ar=2,6-diisopropylphenyl) generate [OCMeCHCMeNAr]SnCl (1) and [OCMeCHCMeNAr] 2 Sn (2) in moderate yield, respectively. Similarly, reacting SnCl 4 with 2equiv. Li[OCMeCHCMeNAr] yields a six-coordinated [OCMeCHCMeNAr] 2 SnCl 2 (3). Divalent tin compound 2 can be oxidized with I 2 in diethyl ether to generate tetravalent tin compound [OCMeCHCMeNAr] 2 SnI 2 (4) in moderate yield. Compounds 1–4 have been characterized by 1 H and 13 C NMR spectroscopy and have been analyzed by X-ray crystallography. Theoretical calculation found that the bonding of ketiminate ligands and tin atom in compound 2 has a strong ionic character.