BACKGROUND This work prepared doped PbO2 electrodes with rare earth oxides, including SnO2–Sb2O5/Ce–PbO2 and SnO2–Sb2O5/Nd–PbO2. We investigated the effect of rare earth oxide dopants on the properties of the PbO2 electrodes, and the application of the electrodes to the synthesis of aromatic aldehydes. RESULTS Scanning electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray analysis and X‐ray photoelectron spectroscopy were used to characterize the surface morphology, crystal structure, elemental content and states of the modified electrodes. The electrodes doped with Ce and Nd have a finer surface, resulting in a larger contact area and increased catalytic oxidation capacity. Cyclic voltammetry and linear sweep voltammetry were also utilized to study the electrochemical response of the modified electrodes. The current efficiency of the prepared redox mediator reached 93.2% through SnO2–Sb2O5/Nd–PbO2 electrode, which was higher than that of other electrodes. Furthermore, the electrode efficiency was basically stable after 10 cycles, which still could reach 88.7%. CONCLUSION It was found that Nd‐doped electrode could enhance indirect anodic oxidation through comparing the effect of SnO2–Sb2O5/PbO2, SnO2–Sb2O5/Ce–PbO2 and SnO2–Sb2O5/Nd–PbO2 electrodes in the application of the synthesis of aromatic aldehydes. © 2023 Society of Chemical Industry (SCI).