Biological removal of nitrate, a highly concerning contaminant, is limited when the aqueous environment lacks bioavailable electron donors. In this study, we demonstrated, for the first time, that bacteria can directly use the electrons originated from the photoelectrochemical process to carry out the denitrification. In such photoelectrotrophic denitrification (PEDeN) systems (denitrification biocathode coupling with TiO photoanode), nitrogen removal was verified solely relying on the illumination dosing without consuming additional chemical reductant or electric power. Under the UV illumination (30 mW·cm, wavelength at 380 ± 20 nm), nitrate reduction in PEDeN apparently followed the first-order kinetics with a constant of 0.13 ± 0.023 h. Nitrate was found to be almost completely converted to nitrogen gas at the end of batch test. Compared to the electrotrophic denitrification systems driven by organics (OEDeN, biocathode/acetate consuming bioanode) or electricity (EEDeN, biocathode/abiotic anode), the denitrification rate in PEDeN equaled that in OEDeN with a COD/N ratio of 9.0 or that in EEDeN with an applied voltage at 2.0 V. This study provides a sustainable technical approach for eliminating nitrate from water. PEDeN as a novel microbial metabolism may shed further light onto the role of sunlight played in the nitrogen cycling in certain semiconductive and conductive minerals-enriched aqueous environment.