A practical, metal-, and additive-free strategy for photo- and electro-induced perfluoroalkylation/cyclization of o-hydroxyaryl enaminones with sodium perfluoroalkanesulfinates under mild conditions has been developed. Various fluoroalkyl chromones were efficiently assembled in moderate to good yields. The scalability of this protocol and the assembling of diverse nitrogen-containing heterocycles from late-stage transformations of fluoroalkyl chromones greatly broaden the practical applications of this developed protocol.