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In this study, an innovative CMS-PbO2 electrode was fabricated by combining hydrothermally synthesized carbon microspheres (CMS) on a PbO2 electrode by electrodeposition. Using CMS-PbO2 electrode, the main factors affecting PRP degradation were studied. Under the optimum process conditions, the concentration of PRP was 50 mg/L, the applied current density was 30 mA/cm2, the electrolyte (Na2SO4) concentration was 0.1 mol/L, and pH value was 7, the PRP degradation rate reached 100%, and chemical oxygen demand (COD) removal rate reached 43.42% after 120 min of electrochemical oxidation. Using field emission scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammetry, linear sweep voltammetry, and electrochemical impedance spectroscopy, the electrochemical performance of the two electrodes was discussed. The composite of carbon microspheres successfully improved the electrochemical activity of the electrode and the electrode conductivity. Furthermore, the ability of the two electrodes to generate hydroxyl radicals was compared and the possible degradation pathway of PRP was speculated. In addition, electrode stability and safety were evaluated by accelerated lifetime experiments and detection of lead ions in solution after electrochemical oxidation. The CMS-electrode was more stable and safer than PbO2 electrode. The CMS-PbO2 electrode provides a new strategy for the treatment of pharmaceutical wastewater.