Organophosphorus compounds (OPCs) are highly important chemicals, finding numerous applications in both academia and industry. Herein we describe a simple photocatalytic method for the stannylation of white phosphorus (P4) using a cheap, commercially-available distannane, (Bu3Sn)2, and anthraquinone as a simple photocatalyst. Subsequent ‘one pot’ transformation of the resulting stannylated monophosphine intermediate (Bu3Sn)3P provides direct, convenient and versatile access to valuable OPCs such as acylated phosphines and tetraalkylphosphonium salts.