The electronic structures of (Vd)Ru(LX)(2) complexes (Vd = 1,5-diisopropyl-3-(2-pyridyl)-6-oxoverdazyl radical; LX = acac or hfac) as neutral, cationic, and anionic species have been investigated experimentally and computationally to probe the interplay between the ruthenium ion and the redox-active verdazyl ligand. The cationic complexes were prepared by oxidation of the corresponding neutral species with silver(I) salts. The hfac-based anionic complex was synthesized by reduction of the neutral species with cobaltocene, but the anionic acac analogue could not be prepared. Experimental (X-ray structures, electronic spectra) and computational (TD-DFT (PCM)) studies reveal that the expression of redox activity of the ligand and metal moieties is highly sensitive to the nature of the ancillary ligands on ruthenium. In the hfac series, the cationic, neutral, and anionic complexes can, respectively, be adequately described as Ru(II) complexes of a coordinated verdazyl cation, neutral radical, and anion. However, the more electron-donating acac coligands facilitate a stronger interaction between ruthenium and verdazyl-via Ru(d) to Vd(pi*) backbonding which is dependent on the overall charge of the complex and has the net effect of creating a high degree of metal-ligand covalency. Studies on the two cationic complexes reveal further distinctions between the acac- and hfac-containing systems: whereas the former has a significant open-shell singlet contribution to the complex ground state, this open-shell formulation is a minor component of the latter.