This work examines the oxygen evolution reaction (OER) taking place on α-PbO2 electrode in methanesulfonic acid (MSA) medium and in sulphuric acid as a comparison, by means of cyclic voltammetry (CVA) and electrochemical impedance spectroscopy (EIS), for soluble lead acid flow battery applications. The influence of MSA concentration on OER is studied. EIS measurements highlighted the impact of the hydrated lead dioxide layer upon decreasing MSA or sulphuric acid concentration. The evolution of the Tafel curves plotted from EIS measurements and quasi-stationary currents while varying acid concentration was interpreted in the light of this hydrated layer which could enhance the electrocatalytic activity when it is thin, and on the contrary act as an electronic barrier when growing for low acid concentration. Both EIS and CVA revealed that OER on lead dioxide is less favoured in MSA than in sulphuric acid. It is finally concluded that a high-concentrated MSA electrolyte is better for lead acid flow battery application in terms of oxygen evolution.