In this work, Ti/PbO2‐MWCNTs anodes modified with different amount with different amount of Tween 80 (0.0–2.0 g/L) were prepared by the direct current electrodeposition method used as anode materials for Zinc electrowinning. The MWCNTs were dispersed in a lead nitrate solution with Tween 80, and the effects of the amount of added Tween 80 on the morphology, phase composition and electrocatalytical performance of lead dioxide coating were investigated. Physical characterizations show that with the increase of the amount of Tween 80, both grain size of PbO2 and carbon content in PbO2 layer firstly increased and then decreased, the preferential orientation and crystallinity of the PbO2 grain growth in the deposition process changed. Electrochemical tests demonstrate that the optimal modified electrode achieved the minimum Eo value and maximum j0 of 2.038 V and 3.781×10−4 A, respectively, an increase of capacitance to 368.8 μF cm−2, and a decrease of charge transfer resistance to 92.74 Ω cm2, which is mainly attributed to the PbO2 electrode modified with Tween 80, coupled with the synergistic effects of MWCNTs doping.