Catalysis by late transition metal complexes is enabled by their facile reversible redox reactivity based on their partially filled d-orbitals. The realization of such redox catalysis by p-block elements is a challenging but rewarding research subject for the advancement in both fundamental main group chemistry and sustainable catalytic technology. In this context, a P(III)/P(V) redox cycle that involves pentacoordinate phosphorane is a competent manifold for applications to catalytic reactions via a formal oxidative addition/transmetalation/reductive elimination sequence. Despite the promising stoichiometric redox reactivity of pentacoordinate organophosphorus compounds, their use in catalytic processes have been primarily limited to oxygen transfer reactions that involve the interconversion between phosphines and phosphine oxides, except for relatively simple, prototypical transformation, such as hydrogenationand reduction of allyl bromides. We report herein on the phosphine-catalyzed hydrovinylation reaction by three-component coupling of acyl fluorides, silyl enol ethers, and alkynoates. The key to the success of the reaction is the formal transmetalation between pentacoordinate P(V) species (i.e., fluorophosphorane) and a silyl enol ether, which allows for C–C bond formation between the polarity-mismatched sites. The bond formation that cannot be attained even by transition metal catalysis is accomplished by a P(III)/P(V) manifold.