The presence of tetracycline (TC) has been detected in the human living environment, and its complex structure makes it difficult to degrade. The green and efficient utilization of electroactivated persulfate advanced oxidation technology for the degradation of tetracycline remains a challenge. In this study, N-doped reduced graphene oxide (N-rGO) was prepared using a hydrothermal treatment method with urea as the nitrogen source. Four different mass ratios of graphene oxide (GO) to urea were synthesized, and the optimal mass ratio was determined through degradation experiments of tetracycline. The N-rGO/EC/PMS three-dimensional electrocatalytic system was constructed, and the influence of the experimental data on TC degradation, such as initial pH, PMS dosage and voltage, was determined. Characterization analysis using scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and other methods was conducted. The efficient catalytic ability of N-rGO was demonstrated through the generation of hydrogen peroxide ( H2O2) and consumption of peroxymonosulfate (PMS). The superiority of the three-dimensional (3D) electrochemical advanced oxidation process was proposed by combining different systems. Furthermore, the presence of hydroxyl radicals (.OH), persulfate radicals ( SO4 ·−), and singlet oxygen (1O2) was identified using electron spin resonance (ESR) technology. The utilization of N-rGO as a three-dimensional electrode, coupled with the advantages of PMS activation and electrochemical oxidation processes, is a promising method for treating organic pollutants in wastewater.