Lead dioxide electrodeposition from methanesulfonic media and physicochemical properties of the resulting oxide were studied in this work to improve anodic process at PbO2/Pb2+ electrode of flow battery. The presence of methanesulfonate ions in the electrodeposition solution causes only a quantitative difference in the PbO2 electrodeposition process without apparently changing the reaction mechanism. In methanesulfonic media PbO2 electrodeposition rate is higher than in nitrate solutions. Current efficiency of PbO2 formation depends on electrode potential (or deposition current density), electrolyte composition (concentration of Pb2+ and methanesulfonate ions), hydrodynamic conditions, pH and temperature of the solution. It is important to note that thick PbO2 coatings (up to 2mm) with good mechanical properties and adhesion to the substrate can be deposited in a wide range of current density (2–100mAcm−2).