In conclusion, we have successfully developed a general and mild photocatalyzed HAT-induced phosphonylation of -C(sp 3 )-H of aliphatic amines. A unique intramolecular HAT-RPC-Arbuzov phosphonylation pathway was devised to effectively address several challenges, including the incompatibility issue between P-reagents and HAT agents, sluggish reactions between alkyl radicals and P-reagents, and the excesses substrates required in intermolecular HAT processes. Central to the success of this protocol is the strategic utilization of a commercially available and easily removable 2-iodobenzoyl group as the intramolecular HAT reagent/protecting group. This facilitates the smooth generation of alkyl radical and enables the oxidativequenching pathway of the PC necessary for the RPC event. This protocol features base-free, redox-neutral, and operationally simple conditions, exhibiting a broad substrate scope for both amines and phosphites. Notably, it allows for the late-stage phosphonylation of complex amine-containing drug molecules, showcasing remarkable functional group tolerance. The protocol is expected to significantly impact the research of aminophosphonic acids in medicinal chemistry due to its generality, robustness, and operational simplicity. We envision its wide adoption in the field, inspiring further advancements and exploration of novel therapeutic agents and compounds for diverse applications.