An efficient oxydifluoroalkylation of hydroxyl-containing alkenes using a copper catalytic system has been developed. This reaction proceeded through a one-pot process of difluoroalkylation followed by nucleophilic attack of the appended hydroxyl group. This strategy has the advantages of a low-cost catalyst and broad substrate scope, which provides a facile access to various fluoroalkylated tetrahydrofurans and tetrahydropyrans.