An electrochemical synthetic strategy to construct P(O)-F bonds was developed via the Atherton-Todd reaction. Promoted by Et4NCl, a series of biologically active phosphoric fluorides were synthesized by use of commercially available P(O)-H feedstocks and Et3N·3HF as the F-source. With this protocol, some potentially functional P(O)-OR and P(O)-SR motifs could also be smoothly forged. This sustainable fluorination approach features step-economy, is chemical-oxidant- and metal-catalyst-free, and offers low cost and mild conditions. Additionally, cyclic voltammetry and control experiments were conducted to propose a reasonable mechanism.