The chemistry of phosphorus is nowadays rivaling that of carbon in terms of complexity and diversity. This tutorial review highlights the state-of-the-art in the field of metal-mediated activation and functionalization of white phosphorus. Particular attention is given to an illustration of the coordination abilities of the intact molecule as well as the disaggregating and reaggregating metal-mediated processes resulting in different polyphosphorus ligands from P(1) to P(12). The metal-promoted P-C and P-H bond forming processes are also reviewed showing that an ecoefficient catalytic protocol for transforming P(4) into high value organophosphorus compounds is a concrete possibility for chemical companies. This tutorial review deals with the activation and functionalization of white phosphorus in the coordination sphere of transition metal complexes. Particular attention is given to the coordination abilities of the intact molecule as well as to the disaggregating and reaggregating metal-mediated processes yielding various polyphosphorus ligands from P(1) to P(12). The metal-promoted processes for P-C and P-H bond formation are also reviewed showing that an ecoefficient catalytic protocol for transforming P(4) into high value organophosphorus compounds offers good opportunities for chemical companies.