The effects of sulfuric acid concentration in VO2+ solutions were investigated via electrochemical methods and electron paramagnetic resonance. Viscosity of solutions containing 0.01 M VOSO4 in 0.1–7 M H2SO4 was measured. Diffusion coefficients were independently measured via electrochemical methods and EPR with excellent agreement between the techniques employed and literature values. Analysis of cyclic voltammograms suggest the oxidation of VO2+ to VO2+ is quasi-reversible at high H2SO4 concentrations (>5 mol/L) and approaching irreversible at lower H2SO4 concentrations. Further analysis reveals a likely electrochemical/chemical (EC) mechanism where the H2SO4 facilitates the electrochemical step but hinders the chemical step. Fundamental insights of VO2+/H2SO4 solutions can lead to a more comprehensive understanding of the concentration effects in electrolyte solutions.