The widespread use of antibiotics and the inefficiency of traditional degradation treatments pose threats to the environment and human health. Previous studies have reported the potential of bio-electro-Fenton (BEF) processes for antibiotic removal. However, some drawbacks, such as a strict pH range of 2-3 and iron sludge generation, limit their large-scale application. Thus, to overcome the narrow pH range of traditional BEF processes, a photo-BEF (PBEF) system was established using a novel FeMn-layered double hydroxide (LDH)/graphitic carbon nitride (g-CN) (FM/CN) composite cathode. The performance of the PBEF system was investigated by degrading tetracycline (TC) under low-power LED lamp irradiation. The results indicated that the pH range of the PBEF system could be expanded to 3-11 using an FM/CN cathode, which exhibited a TC removal efficiency of 63.0%-75.9%. The highest TC removal efficiency was achieved at pH 7. The efficient mineralization of TC by the PBEF system can be high, up to 67.6%. In addition, the TC removal mechanism was discussed in terms of reactive oxygen species, TC degradation intermediate analyses, and density functional theory (DFT) calculations. Strong oxidative hydroxyl radicals (·OH) were the dominant reactive oxidizing species in the PBEF system, followed by ·O and h. Three pathways of TC degradation were proposed based on the analysis of intermediates, and the reactive sites attacked by electrophilic reagents were explored using DFT modeling. In addition, the overall toxicity of TC degradation intermediates effectively decreased in the PBEF system. This work offers deep insights into the TC removal mechanisms and performance of the PBEF system over a wide pH range of 3-11.