A two-step catalyst-free procedure for the construction of 3-perfluoroalkyl-2-(phosphoryl)methyl furans from commercially available 1-perfluoroalkyl 1,3-diketones is reported. Propargylic alcohols, prepared by direct alkynylation of the diketones, react with PCl₃ via [2,3]-sigmatropic rearrangement – enolate cyclization sequence, leading to multifunctional furans. The reaction mechanism is supported by DFT study. In addition, the bioactivity modifying effect of phosphoryl group on 3-perfluoroalkyl furans is depicted. (Figure presented.).