The electrochemical performances of deposited MnO2 on lead alloy anode by pulse current (PC) and direct current (DC) electrodeposition in manganese sulfate solution were investigated by performing measurements of galvanostatic polarization, cyclic voltammetry (CV), and Tafel tests. The composition and morphology of MnO2 were observed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The anode deposited with MnO2 layers by PC electrodeposition presented a lower anodic potential of 60 mV and more uniform potential oscillating attractor with fractal dimension of 1.0337 compared with those of DC electrodeposition. In addition, MnO2 layers exhibited excellent corrosion resistance because less intermediate oxide Mn(III) appeared in anode deposits. Furthermore, the cathodic current efficiency improved by 3.11∼3.77% and energy consumption decreased by 5.30∼8.17% after galvanostatic electrolysis for 2∼8 h by using PC instead of DC for manganese metal electrodeposition. As an external control method, PC electrodeposition not only regulated the structure and surface morphology of MnO2 but also affected the anode electrochemical behaviors and cathode manganese metal deposition. Electrochemical oscillations and other characteristics of anode reaction described in this study could inspire future work on promoting the whole electrowinning process.