An octahedral ruthenium(III) Schiff base complexes of the type [RuX(EPh₃)(L)] (where, X=Cl/Br; E=As/P; L=dianion of the Schiff bases derived from acetoacetanilide with o-phenylenediamine and salicylaldehyde/o-hydroxyacetophenone/o-vanillin/2-hydroxy-1-naphthaldehyde) have been synthesized from the reactions of equimolar reactions of [RuX₃(EPh₃)₃] and Schiff bases in benzene. The new Ru(III) Schiff base complexes have been characterized by elemental analyses, FT-IR, electronic, ¹H NMR and ¹³C NMR spectra, EPR spectral studies, powder X-ray diffraction (XRD) and electrochemical studies. The new complexes were found to be effective catalysts for aryl–aryl coupling and the oxidation of alcohols into their corresponding carbonyl compounds, respectively, using molecular oxygen atmosphere at ambient temperature. Further, the new Ru(III) Schiff base complexes were screened for their antibacterial activity against Pseudomonas aeruginosa, Vibrio cholera, Salomonella typhi and Staphylococcus aureaus.