Numerous crystal structures of donor-stabilized LiX species are known, but only two of them show a heterocubane arrangement [LiX(Do)](4) (X = Cl, Br; Do = donor) in the solid state. Herein we report the X-ray crystal structure of [LiI(NEt3)](4) (1), obtained by the reaction of LiN(SiMe3)(2) with either Gal or AII in the presence of NEt3, The structural backbone of 1 is a [LiI](4) heterocubane core, which is compared to [LiX](4) (X = Cl, Br) as well as to [Li(CH3)](4) The energetics of the formation of I and its stability with respect to solid LiI is rationalized and additionally supported by DFT (density functional theory) calculations.