The invention discloses a fluoroalkylation method using phenol and phenol derivatives as photocatalysts in the field of organic synthesis. In particular, according to the method, simple and easily available olefin, alkyne and iodofluoroalkyl compounds are adopted as raw materials, and inexpensive and easily available chemical raw material phenol and phenol derivatives are innovatively used as catalysts so as to obtain a plurality of fluoroalkyl-substituted olefin and fluoroalkyl-substituted alkane and derivatives of the fluoroalkyl-substituted olefin and fluoroalkyl-substituted alkane in highyield under the irradiation of visible light. The method has a green reaction and good atomic economy, and has excellent functional group compatibility and high stereoselectivity at the same time. Thenovel catalytic system can be applied to a wide range of reaction types, and the resulted products are widely used in life sciences, medicine and materials science; and for allyl phenol and other substrates of an olefin structure with phenolic hydroxyl groups, no additional addition of phenolic catalysts is required, and the fluoroalkylated product can be obtained selectively through change of the solvent and base of the reaction system.