We performed an extensive study on Nafion 117 membrane imbibed with various concentrations of aqueous ammonium metavanadate (NH4VO3), and vanadyl sulfate (VOSO4), in 2 M H2SO4 over the temperature range of 20–100 °C, using 1H NMR and AC Impedance spectroscopies. The objective was to determine the effect of the tetravalent (VO2+) and pentavalent (VO2 +) vanadium ions on the proton transport of Nafion 117.1H NMR chemical shift and linewidth data show greater short-range proton transport for the VO2 + imbibed membranes compared with the VO2+. However, the local environments seem to differ in that while the data for VO2 + imbibed membranes seem to follow more the trends observed for water hydrated Nafion 117, those for the VO2+ followed the trend of its aqueous bulk vanadium solvents, indicating that viscosity plays a larger role for the VO2+ imbibed membranes compared to the VO2 +.