An -diimine-stabilized AlAl-bonded compound [L²⁻Al^IIAl^IIL²⁻] (L=[{(2,6-iPr₂C₆H₃)NC(Me)}₂]; 1) consists of dianionic -diimine ligands and sub-valent Al²⁺ ions and thus could potentially behave as a multielectron reductant. The reactions of compound 1 with azo-compounds afforded phenylimido-bridged products [L⁻Al^III(μ₂-NPh)(μ₂-NAr)Al^IIIL⁻] (2–4). During the reaction, the dianionic ligands and Al²⁺ ions were oxidized into monoanions and Al³⁺, respectively, whilst the [NAr]²⁻ imides were produced by the four-electron reductive cleavage of the NN double bond. Upon further reduction by Na, the monoanionic ligands in compound 2 were reduced to the dianion to give [(L²⁻)₂Al^III₂(μ₂-NPh)₂Na₂(thf)₄] (5). Interestingly, when asymmetric azo-compounds were used, the asymmetric adducts were isolated as the only products (compounds 3 and 4). DFT calculations indicated that the reaction was quite feasible in the singlet electronic state, but the final product with the triplet-state monoanionic ligands could result from an exothermic singlet-to-triplet conversion during the reaction process.