Oxidation of carbene-stabilized diarsenic, L:As-As:L [L: = :C{N(2,6-(Pr2C6H3)-Pr-1)CH}(2)] (1), with gallium chloride in a 1:4 ratio in toluene affords the dicationic diarsene complex [L:As = As:L](2+)([GaCl4](-))(2) (2(2+)[GaCl4](2)), while oxidation of 1 with GaCl3 in a 1:2 ratio in Et2O yields the monocationic diarsenic radical complex [L:AsAs:L](center dot+)[GaCl4](-) (2(center dot+)[GaCl4]). Strikingly, complex 2(center dot+) is the first arsenic radical to be structurally characterized in the solid state. The nature of the bonding in these complexes was probed computationally and spectroscopically.