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 (1) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa)P (3) is presented, and its subsequent selective derivatization with Brønsted acids, MeOTf, PhECl (E = P, As), and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes.