A light-triggered, Ni-catalyzed cyanation of aryl triflates was herein reported, which provides a benign photochemical synthesis of aryl nitriles using 1,4-dicyanobenzene as the CN source instead of HCN or a metallic CN source. This mild method uses a readily available bisphosphine ligand and a soluble organosilicon reagent as the reductant and is carried out under purple light without an external photocatalyst. This cyanation was effective for aryl triflates derived from phenols and bisphenols as well as lignin-derived phenolic compounds, demonstrating its potential utility for the synthesis of aryl nitriles from biomass.