Graphite–lead dioxide electrodes doped with rare earth Cerium (Ce-PbO2/C electrodes) were prepared by electrodeposition. The scanning electron microscope results showed that the microstructure and crystal orientation of electrode surface were changed by Cerium doping. CeO2 was detected from modified electrodes by X-ray diffraction analysis. The cyclic voltammetry spectra indicated that the oxidation peak potential of cerium-doped electrode was smaller than pure PbO2 electrode. Effects of the novel electrode on acid red B degradation were evaluated systematically under different parameters, including applied voltage, initial pH, supporting electrolyte concentration, electrode spacing, and influent concentration. The results indicated that chemical oxygen demand, decolorization, and ammonia nitrogen removal rate of Ce-PbO2/C electrodes reached 90.17, 99.98, and 97.23 %, respectively, after 60-min electrolysis at initial 1000 mg L−1 acid red B concentration. The possible mechanism of acid red B degradation over Ce-PbO2/C electrodes was monitored by gas chromatography-mass spectrometer.