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 α-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.