An α‐diimine‐stabilized AlAl‐bonded compound [L2−AlIIAlIIL2−] (L=[{(2,6‐iPr2C6H3)NC(Me)}2]; 1) consists of dianionic α‐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−AlIII(μ2‐NPh)(μ2‐NAr)AlIIIL−] (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−)2AlIII2(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.