A visible-light-driven, photocatalyst-free route starting from easily accessed ortho-hydroxycinnamic esters and O-perfluoropyridin-4-yl oximes has been successfully developed to rapidly assemble a wide range of 3-cyanoalkyl coumarins. This process does not require addition of external photocatalysts, exhibiting beneficial features including mild reaction conditions, synthetic simplicity, and excellent substrate compatibility. Extensive mechanistic investigations revealed that the in situ generated phenolate anions served as photosensitizers to drive this photoinduced transformation.