A new series of octahedral Ru(III) complexes of the type [Ru (Cl)2 (DMAPIMP-X) (EPh3)2]; DMAPIMP={2-[(4-N,N’-dimethylaminophenylimino)-methyl]-4-X-phenol}; X = Cl, Br or I; E = P or As) have been prepared and characterized by spectral, magnetic and cyclic voltammetric studies. The Ru (III) complexes are low spin and paramagnetic with one unpaired electron. These complexes absorb strongly in the visible region owing to the metal to ligand charge transfer (MLCT) transition. The IR spectral data reveals that the monobasic bidentate Schiff base ligands are chelated to ruthenium through the imine nitrogen and the deprotonated phenolic oxygen. The three line e.s.r spectrum of RuIII complexes with gx ≠ gy ≠ gz indicates magnetic anisotropy and an asymmetry in the electronic environment around the Ru atom. All Ru(III) complexes display the redox couple in the range – 0.826 to – 0.971 V. Further more the DNA binding experiment of the complexes were carried out by UV–Vis absorption spectral titration and the binding constant Kb = 1.2 ± 0.3 × 104 M−1 to 4.4 ± 0.3 × 104 M−1 have been found. The hyperchromism with moderate red shift of 2–4 nm, such a small change in λmax is more in keeping with groove binding, leading to small perturbations.