An intriguing visible-light-induced strategy has been established for the P-H insertion reaction between acylsilanes and H -phosphorus oxides that, upon a subsequent acidic process, deliver a wide variety of α-hydroxyphosphorus oxides in good yields (up to 93% yield). The metal-free protocol represents a unique example of P-H insertion for C-P bond formation through in situ generation of siloxycarbenes. This methodology features the advantages of operational simplicity, mild conditions, broad substrate scope, and column free in gram-scale synthesis.