An intriguing P-H insertion of arylhalodiazirines with H-phosphorus oxides under ultraviolet-light irradiation is described. This methodology provides an efficient and straightforward route to the construction of a variety of α-halophosphorus oxides in good yields (≤95%), which represents a unique example of P-H insertion of α-halocarbenes for C-P bond formation. The metal-free protocol features the advantages of mild reaction conditions, high atom economy, and environmental friendliness.