We propose and demonstrate the novel concept of synthesizing organophosphorus compounds directly from black phosphorus (BP) nanoparticles as the feedstock. Compounds such as alkyl phosphines, alkyl phosphine oxides, phosphine sulfide, and hexafluorophosphate anion are prepared with good isolation yields under mild conditions. Selective synthesis of primary, secondary, and tertiary organophosphorus compounds is also demonstrated utilizing this one-pot approach. Reaction mechanisms are proposed and discussed. Compared with traditional white phosphorus (P4)-based methods, the new synthetic concept and process utilizing elemental phosphorus are more efficient and environmentally friendly.