A convenient synthetic route to Ga-stabilized pnictogen-centered radicals and gallapnictenes by manipulation of pnictogen–carbon bond strengths is presented. Two equivalents of LGa (L = HC[C(Me)N(Dip)]₂, Dip = 2,6-i-Pr₂C₆H₃) react with Cp^ArAsCl₂ (Cp^Ar = C₅(4-t-BuC₆H₄)₅) with formation of the arsenic-centered radical [L(Cl)Ga]₂As·1. In contrast, the analogous reaction with TerSbCl₂ (Ter = 2,6-Mes₂C₆H₃; Mes = 2,4,6-Me₃C₆H₂) yields the gallastibene LGa═SbTer (2) containing a Ga–Sb double bond, whereas reactions of DipSbCl₂ with one and two equivalents of LGa give the monoinsertion and bisinsertion products L(Cl)GaSb(ClDip) (3) and [L(Cl]Ga]₂SbDip (4), respectively. 1–4 were structurally characterized by single crystal X-ray diffraction. The description of 1 as an arsenic-centered radical is consistent with results of electron paramagnetic resonance and density functional theory (DFT) studies. The π-bonding in LGa═SbTer (2) is estimated to 10.68 kcal mol^–1 by variable-temperature (VT) NMR spectroscopy, and DFT studies reveal a significant π-bonding interaction between Sb and Ga.