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 polyphosphanes in addition to the known monoinserted product LGaP 4 (1) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa) 2P 6 (3) is presented, and its subsequent selective derivatization with Brønsted acids, MeOTf, Ph 2ECl (E = P, As), and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes.