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The dual-chamber photoelectrocatalytic (PEC) system possess advantages in the degradation efficiency and processing cost of organic contaminants. In this study, TiO 2 nanotube arrays modified by rGO and g-C 3 N 4 (rGO/g-C 3 N 4 /TNAs) photoelectrodes were successfully prepared. The surface micromorphology, chemical structure, crystal structure, and basic element composition of rGO/g-C 3 N 4 /TNAs photoelectrodes were studied by SEM, FTIR, XRD, Raman, and XPS. UV–vis absorption, photoluminescence (PL) spectra, and photoelectrochemical (PECH) tests were used to explore the photoelectrochemical characteristics of rGO/g-C 3 N 4 /TNAs photoelectrodes. Under simulated sunlight illumination, the dual-chamber PEC system with external bias voltage was used to investigate the degradation of oxytetracycline (OTC) on rGO/g-C 3 N 4 /TNAs photoelectrodes. The results showed that rGO and g-C 3 N 4 were successfully loaded on TNAs, and the separation efficiency of electrons and holes at rGO/g-C 3 N 4 /TNAs photoelectrodes was improved. The light absorption range of rGO/g-C 3 N 4 /TNAs photoelectrodes extends to the visible light region and has better light absorption performance. Compared with the photocatalytic process, when 1.2 V bias voltage was applied, the degradation efficiency of OTC in anode and cathode chambers in PEC were increased by 3.28% and 44.01% within 60 min, respectively. In addition, the anode and cathode chambers have different degradation effects on OTC. Both the external bias voltage and initial pH have significant effects in cathode chamber, but have little effect in photoanode chamber. The fluorescence excitation-emission matrix spectra and liquid chromatography-tandem mass spectrometry showed that there were different intermediates in the degradation process of OTC. This study indicated that for the dual-chamber PEC system, rGO/g-C 3 N 4 /TNAs photoelectrodes exhibited excellent photocatalytic performance and have potential application prospects in water environmental remediation. [Display omitted] • The novel ternary rGO/g-C 3 N 4 /TNAs photoelectrodes were prepared. • The photoelectrodes showed superior photoelectrocatalytic activity. • Oxytetracycline can be efficiently degraded by rGO/g-C 3 N 4 /TNAs photoelectrodes. • Degradation of oxytetracycline was enhanced in the dual-chamber system. [ABSTRACT FROM AUTHOR]