An efficient and mild method for the direct phosphorylation of phenols, alcohols, and amines with P(O)–H has been reported by LiI/TBHP mediated oxidative cross‐coupling reaction. Moreover, this protocol extended to β‐keto esters for the synthesis of enol phosphates using H‐phosphonates. Notably, this developed method applied for the synthesis of organopesticides such as paraoxon, cyanophos, and methyl parathion. The key features of this protocol are mild conditions, short reaction time, good functional group tolerance, and broad substrate scope.