Two equivalents of LGa (L=HC[C(Me)N(2,6‐iPr₂C₆H₃)]₂) reacted with PX₃ (X=Cl, Br) with insertion into two P−X bonds and formation of [L(X)Ga]₂PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl₃ occurred with twofold insertion and subsequent elimination of LGaCl₂ and formation of the Ga‐substituted diarsene [L(Cl)Ga]₂As₂ (3). Analogous findings were observed in the reactions with Me₂NAsCl₂, yielding the unsymmetrically‐substituted diarsene [L(Cl)Ga]As=As[Ga(NMe₂)L] (4). The reaction of As(NMe₂)₃ with LGa gave [L(Me₂N)Ga]₂As₂ (5) after heating at 165 °C for five days, whereas the reaction with LAl gave [L(Me₂N)Al]₂As₂ (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt₂)₃ to give [L(Et₂N)Ga]₂Bi₂ (7). Complexes 1–7 were characterized by NMR spectroscopy (¹H, ¹³C, ³¹P), elemental analysis, and single‐crystal X‐ray diffraction (except for 1 and 5). The bonding situations in 4, 6, and 7 were analyzed by quantum chemical calculations.