Here we developed an efficient Ni-catalyzed C–F bond phosphorylation of arylfluorides via the crucial intermediates of P–P(O) and P(O)OR. P–P(O) mediated organophosphorus generation is observed for active arylfluorides, whereas inactive arylfluorides can also be activated and phosphorylated via a P(O)OR-mediated pathway, which is barely reported yet. Facile scale-up to the gram level and the upgrading