Asymmetric hydrophosphorylation of unsaturated compounds is a straightforward and atom-economic approach to obtain chiral organophosphorus compounds. Herein, we describe a ligand-controlled regiodivergent and enantioselective hydrophosphorylation of styrenes facilitated by Pd catalysis and a PC-Phos ligand. This methodology enables the facile synthesis of both Markovnikov and anti-Markovnikov alkyl phosphorus compounds with high to excellent regio- and enantioselectivity, achieving up to >95:5 rr and 92% ee. Deuterium-labeling experiment and computational mechanistic studies unveil that the migratory insertion is the enatio-determining step, in which the O···H hydrogen bonding between the H-phosphonate and the ligand is identified as a crucial factor. Furthermore, our investigations demonstrate that both migratory insertion and reductive elimination contribute to achieving high regioselectivity and enantioselectivity. These findings not only advance the field of asymmetric hydrophosphorylation of simple styrenes, but also deepen our understanding of noncovalent interactions in ligand design.