The reaction of LGa (L = Dipp(4-(Dipp-imino)-pent-2-en-2-yl)amide; Dipp: 2,6-diisopropylphenyl) and white phosphorus was revisited. A plethora of unprecedented poly-phosphanes in addition to the known monoinserted product LGaP4 (1) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa)(2)P-6 (3) is presented, and its subsequent selective derivatization with Bronsted acids, MeOTf, Ph2ECl (E = P, As); and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes.