In this work, particles of activated carbon supported by Fe-N-TiO2 (Fe-N-TiO2/AC) were synthesized and used as the three-dimensional (3D) particle electrode for folic acid wastewater treatment in the 3D electrolysis and photocatalysis coupling process. The structure, morphology, and physical and electrochemical properties of the Fe-N-TiO2/AC particles were characterized, and the results showed that Fe-N-TiO2 was bound on the surface of AC particles by chemical attachment, and the Fe-N-TiO2/AC particles had better capability of adsorption and charge transfer as compared with the TiO2/AC particles. The effects of key operating parameters in the reaction process, including the current density (optimum 0.6 mA/cm2), aeration (optimum 5 L/min), pH value (optimum 5) and the ratio of Fe-N-TiO2/AC particles to cellulose acetate film coating AC particles (optimum 4:1), were optimized regarding the total oxygen carbon (TOC) removal. Under the optimum conditions, TOC removal from folic acid wastewater reached 82.4% during 120 min photoelectrocatalysis. The kinetic analysis and mechanism study showed that the degradation process fitted to the second-order kinetic model better than to the first-order, and the system exhibited synergistic effects in inhibiting photogenic electron-hole recombination and improving electrolytic efficiency. At the same time, this system has the ability to overcome the interference of the strong ionic strength in folic acid wastewater.