In this study, a self-biased bio-photoelectrochemical system (SB-BPES) was constructed using a bioanode and the g-C3N4/CdS heterojunction photocathode for nitrofurazone (NFZ) degradation under solar irradiation. The physio-chemical properties and optical performance of photocatalysts were characterized, and photo-electrochemical properties of various photocathodes were analyzed. Results showed that g-C3N4/CdS exhibited the broadest visible light absorption range (to 594 nm) and the most efficient e--h+ separation; and its corresponding photocathode showed the highest photocurrent (9.8 μA), and the lowest charge transfer resistance (5.43 ☓ 103 Ω). In the solar-illuminated SB-BPES with g-C3N4/CdS photocathode, about 80% of NFZ removal rate was achieved within 10 h. More importantly, TOC removal of 62.6% was achieved in 24 h, which was 1.8 times of that from the open circuit SB-BPES, and 4.3 folds of that from microbial degradation; also, about 1.5 times of those from SB-BPES with g-C3N4 and CdS photocathodes. Besides, reproducible current generations (∼1.0 mA) were produced. These verified that it was a self-sustained system for spontaneously pollutants degradation and electricity generation. Moreover, possible degradation mechanism and pathways were proposed according to the identified intermediates. This study provides inspiration for synchronic improving refractory organics degradation and net energy recovery.