In this study, we investigated the impact of ancillary ligands on the anticancer activity of benzodipyridophenazine-based Ru(II) and Ir(III) complexes (Ru1, Ru2, Ir1, and Ir2). These metal complexes displayed three significant absorption bands attributed to the ligand-centered (LC) transitions, ligand-to-ligand charge transfer (LLCT), and metal-to-ligand charge transfer (MLCT). Binding studies of biomolecules were performed with the complexes along with the ligand, and it was found that after binding with Ru(II)/Ir(III), the properties of the ligands were enhanced.