Vanadium(III) complexes bearing salicylaldiminato ligands (2a−k) [RN═CH(ArO)]VCl2(THF)2 (Ar = C6H4, R = Ph, 2a; p-CF3Ph, 2b; p-CH3Ph, 2c; 2,6-Me2Ph, 2d; 2,6-iPr2Ph, 2e; cyclohexyl, 2f; Ar = C6H3tBu(2), R = Ph, 2g; 2,6-iPr2Ph, 2h; Ar = C6H2tBu2(2,4), R = Ph, 2i; 2,6-iPr2Ph, 2j; Ar = C6H2Br2, R = Ph, 2k) were prepared from VCl3(THF)3 by treating with 1.0 equiv of (RN═CH)ArOH in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA). The reaction of VCl3(THF)3 with 2.0 equiv of (RN═CH)ArOH in THF in the presence of excess TEA afforded vanadium(III) complexes bearing two salicylaldiminato ligands (3a−k), [RN═CH(ArO)]2VCl(THF)x (Ar = C6H4, x = 1, R = Ph, 3a; p-CF3Ph, 3b; p-CH3Ph, 3c; 2,6-Me2Ph, 3d; 2,6-iPr2Ph, 3e; cyclohexyl, 3f; Ar = C6H3tBu(2), x = 1, R = Ph, 3g; x = 0, 2,6-iPr2Ph, 3h; Ar = C6H2tBu2(2,4), x = 1, R = Ph, 3i; 2,6-iPr2Ph, x = 0, 3j; Ar = C6H2Br2, x = 1, R = Ph, 3k). These complexes were characterized by FTIR and mass spectra as well as elemental analysis. Structures of complexes 2a...