This review covers recent progress in the activation of white phosphorus, P_4, researched in the past ten years. Activation of the small molecule P_4 is a very complicated process. When reacts with transition metal complexes, the tetrahedral P_4 can retain its geometry and coordinate to a metal center via a η^1 fashion. Upon activation, white phosphorus can not only be split into smaller ligands P_3, P_2 or P when P_4 is reduced by transition metal complexes, but also form poly-phosphorus ligands via oligermization.