In the presence of chloride abstractors, metal-coordinated chlorophosphines undergo facile room-temperature electrophilic substitution reactions with unsaturated organic substrates, leading to P-C bond formation. This methodology can be applied sequentially two or three times, stepwise or in one-pot reactions, to form phosphines with three different substituents. The reactions are rapid and high-yielding, and can be applied to a wide range of organic substrates, making them valuable tools for P-C bond formation.