The anodic electrodeposition of polyaniline (PANI) on Pb substrate was performed by both potentiostatic and galvanostatic method. Influences of the applied potential and current density on the formation of PANI were investigated. The electrocatalytic effect of Pb electrode modified by PANI on the oxygen evolution reaction (OER) in sulfuric acid was examined via anodic polarization measurements. The results indicated that a significantly enhanced catalytic activity was obtained on Pb electrodes modified by PANI. The overpotential for OER drops 0.14V~0.42V and the exchange current density rises by one to three orders of magnitude compared to the blank Pb electrode. As a new kind of OER anodes in acidic electrolytes, the Pb electrode coated by PANI shows a potential application prospect in the electrowinning of non-ferrous metals.