Reactions of ruthenium(II) carbonyl complexes of the type [RuHCl(CO)(PPh3)2(B)] [B = PPh3, pyridine (py), piperidine (pip) or morpholine (mor)] with bidentate Schiff base ligands derived from the condensation of 2-hydroxy-1-naphthaldehyde with aniline, o-, m- or p-toluidine in a 1 : 1 mol ratio in benzene resulted in the formation of complexes formulated as [RuCl(CO)(L)(PPh3)(B)] [L = bidentate Schiff base anion, B = PPh3, py, pip, mor]. The complexes were characterized by analyses, IR, electronic and 1H NMR spectroscopy, and cyclic voltammetric studies. In all cases, the Schiff bases replace one molecule of phosphine and a hydride ion from the starting complexes, indicating that Ru–N bonds in the complexes containing heterocyclic nitrogenous bases are stronger than the Ru–P bond to PPh3. Octahedral geometry is proposed for the complexes.