The article dealt with the ruthenium complexes of redox active azo appended modified lawsone L 1 À (HL 1 : (E)-2hydroxy-3-(p-tolyldiazenyl)naphthalene-1,4-dione))/L 2 À (HL 2 :5-À and L 2 À differed with respect to the para-quinone versus phenazine moieties linked to the azo function. Structural analysis of the complexes established unreduced state of the azo (N=N) group of coordinated L 1 À /L 2 À or pap as well as unprecedented para-quinone form of L 1 À . The involvement of selective redox center(s) towards the accessible redox steps of the complexes encompassing multiple redox active entities i. e. Ru, phenolate (L 1 À /L 2 À ), para-quinone (L 1 À ), phenazine (L 2 À ), azo (L 1 À /L 2 À , pap), diimine (bpy) was analyzed by combined experimental and DFT calculations. It revealed that under the prevailing competitive scenario oxidation was mostly dominated by the phenolate group of L 1 À /L 2 À (phenolate!phenoxide), while successive reductions were taken place either at the para-quinone/phenazine units of L 1 À /L 2 À or azo/diimine functions of pap/bpy. Though the azo function of pap in 3 + /7 + underwent facile reduction, the same azo function associated with L 1 À /L 2 À conspicuously remained unreduced in all occasions. The frontier molecular orbital analysis revealed that the propensity of pap for the azo reduction with special reference to that in L 1 À /L 2 À could be correlated with its relatively lower energy π* orbital (LUMO). Complexes displayed intense LMCT (1/5) and bpy (2 + /6 + ), pap (3 + /7 + ), L (4/8) targeted MLCT transitions in the visible region.