The existence of β-naphthoxyacetic acid (BNOA) pesticide in water system has aroused serious environmental problem because of its potential toxicity for humans and organisms. Therefore, exploiting an efficient method without secondary pollution is extremely urgent. Herein, a promising Ti/PbO2-Co-Pr composite electrode has been successfully fabricated through simple one-step electrodeposition for efficiently electrocatalytic degradation of BNOA. Compared with Ti/PbO2, Ti/PbO2-Co and Ti/PbO2-Pr electrodes, Ti/PbO2-Co-Pr electrode with smaller pyramidal particles possesses higher oxygen evolution potential, excellent electrochemical stability and outstanding electrocatalytic activity. The optimal degradation condition is assessed by major parameters including temperature, initial pH, current density and Na2SO4 concentration. The degradation efficiency and chemical oxygen demand removal efficiency of BNOA reach up to 94.6% and 84.6%, respectively, under optimal condition (temperature 35 °C, initial pH 5, current density 12 mA cm-2, Na2SO4 concentration 8.0 g L-1 and electrolysis time 3 h). Furthermore, Ti/PbO2-Co-Pr electrode presents economic energy consumption and superior repeatability. Finally, the possible degradation mechanism of BNOA is put forward according to the main intermediate products identified by liquid chromatography-mass spectrometer. The present research paves a new path to degrade BNOA pesticide wastewater with Ti/PbO2-Co-Pr electrode.