Sunlight plays an important role in transforming effluent organic matter as wastewater effluents travel downstream, but the corresponding effects on the formation of haloacetonitriles (HANs), a group of toxic disinfection byproducts, in wastewater-impacted surface water has not been thoroughly investigated. In this study, we observed that sunlight preferentially attenuated the formation potential of bromochloroacetonitrile (BCAN-FP) over that of dichloroacetonitrile (DCAN-FP) in chlorine- and UV-disinfected secondary effluents. For four effluent samples from different plants, 36 h irradiation by simulated sunlight removed 28%-33% of DCAN-FP and 41%-48% of BCAN-FP. Across a larger set of effluent samples (n = 18), 8 h irradiation (equivalent to 2-3 d of natural sunlight) decreased the calculated cytotoxicity contributed by dihaloacetonitrile-FP in most samples. Similar behavior was observed for a mixture of wastewater and surface water (volume ratio 1:1). For UV-disinfected effluents, the higher the UV dose, the more likely was there a reduction in DCAN-FP and BCAN-FP in the subsequent sunlight irradiation. Experiments with model compounds showed that fulvic acid and UV photoproducts of tryptophan yield excited triplet state organic matters during sunlight irradiation and play an important role in promoting the attenuation of HAN precursors.