A series of new hexa-coordinated ruthenium(III) complexes of the type [RuX(Nap-o-phd)(EPh 3 )] (where, H 2 -Nap-o-phd=N,N′-bis(2-hydroxy-1-naphthaldehyde) o-phenylene diamine; X=Cl or Br; E=P or As) have been prepared by reacting [RuX 3 (EPh 3 ) 3 ] and [RuBr 3 (PPh 3 ) 2 (MeOH)] (where X=Cl or Br; E=P or As) with tetradentate Schiff base ligand (H 2 -Nap-o-phd) in 1:1 molar ratio. The complexes have been characterized by elemental analyses, infra red, electronic, electron paramagnetic resonance spectroscopy and cyclic voltammetry. The coordination geometry and structure of the complexes have been investigated by extended X-ray absorption fine structure (EXAFS) spectroscopy and an octahedral structure has been proposed.