Electronic effects of one-electron reduction are investigated for (OV)TPP (vanadyltetraphenylporphine) by the use of spectroelectrochemical techniques. Cyclic voltammetry (CV), absorption, and resonance Raman (RR) spectroscopy of the anion radical are analyzed with the aid of isotope labeling and normal-coordinate analysis (NCA) in order to understand the structural changes. The first reported Q-band excitation RR spectra of the (OV)TPP anion radical provide important information regarding the structural distortion of the porphyrin ring upon one-electron reduction, through detection of A2g modes. Direct evidence for static distortion of the porphyrin ring is provided by the lowered depolarization ratios of the A2g modes. Moreover, the upshift of the ν19 vibrational mode establishes that some of the Cα-C m bonds are strengthened in the anion. Consideration of the molecular orbital pattern shows this observation to be consistent with a B1g and not a B2g Jahn−Teller distortion. The normal-mode calculation supports this inference.