A K2S2O8/Cu(OAc)(2)-mediated oxidative C-H/P-H cross coupling of aldehyde hydrazones with diphenylphosphine oxide for the direct preparation of functionalized alpha-iminophosphine oxides is reported. The reaction shows good functional group tolerance and proceeds smoothly under mild conditions. This strategic protocol for C-P bond formation is facilitated by a net oxidative aminyl radical polar crossover process.