Fulvic acid (FA) is a representative photosensitive dissolved organic matter (DOM) compound that occurs naturally in paddy soils. In this study, the effect of a FA + nitrate treatment (0, 4 and 8 mg/L FA + 20 mmol/L nitrate) on denitrification and As(III) immobilization in flooded paddy soils was assessed under dark and intermittently illuminated conditions (12 h light+12 h dark). The FA input stimulated denitrification in illuminated soils (~100 % of nitrate removal within 6 days) compared to dark conditions (~92 % nitrate removal after 6 days). Meanwhile, As(III) (initial concentration of 0.1 mmol/L) was nearly completely immobilized (~100 %) under illuminated conditions after 4 days for the FA + nitrate treatment compared to 90– 93 % retention in the dark. Denitrification and As immobilization were positively related to the FA dosage in the illuminated assays. The stronger denitrification in illuminated soils was ascribed to denitrifiers harvesting photoelectrons from photosensitive substrates/semiconducting minerals. FA addition also increased the activities of denitrifying enzymes (e.g., NAR, NIR and NOR) and the denitrification electron transport system by nearly 0.6–0.7 and 1.5–1.8 times that of the nitrate-alone treatment under illuminated and dark conditions, thereby fostering stronger denitrification. Upon irradiation, As(III) immobilization was not only stimulated by the interactions with the denitrification pathway whereby As(III) acts as an electron donor for denitrifiers, but was also modulated by Fe(III)/oxidative reactive species-derived photooxidation of As(III). Moreover, the FA + nitrate treatment promoted the enrichment of metal-oxidizing bacteria (e.g., Stenotrophomonas and Acidovorax) that are responsible for nitrate-dependent As(III)/Fe(II) oxidation. The results of this study enhance our understanding of interactions among the biogeochemical cycles of As, Fe, N and C, which are intricately linked by a biophotoelectrochemical pathway in flooded paddy soils. © 2023