Chlorophenylglyoxime and Ligand Complexes ([M(Salen/Salophen)]2O, [M(Saldeta/Salpy)Cl] shortened as LC, M = Fe(III) or Cr(III)) have been synthesized. 3,5-dicarboxyanilinophenylglyoxime (5) and 4-carboxyphenylhydrazinophenylglyoxime (6) have been synthesized with the reaction of chlorophenylglyoxime and 5-aminoisophtalalic acid or 4-hydrazinobenzoic acid. [M(Salen/Salophen/Saldeta/Salpy)-3,5-dicarboxyanilinophenyl-glyoxime)] (7–14) or [M(Salen/Salophen)-4-carboxyphenylhydrazinophenylglyoxime)] (15–22) have been synthesized from (5) or (6) and LCs. The new heterotrinuclear and pentanuclear complexes (23–38) have been obtained from (7–22) and Ni(II) salt. Then, heteronuclear and BF2 + capped vic-dioxime complexes (39–54) have been synthesized. The complexes have been characterized as low-spin (S = 1/2) distorted octahedral [FeIII(Salen/Salophen)], high-spin (S = 5/2) distorted octahedral [FeIII(Saldeta/Salpy)] and (S = 3/2) distorted octahedral [CrIII(Salen/Salophen/Saldeta/Salpy)] bridged by COO− groups. The structure of all ligand and complexes were identified by using elemental analysis, thermal analyses, magnetic susceptibility, LC-MS, ICP-AES, 1H-NMR and FT-IR spectral data.