High-resolution X-ray diffraction data of triisobutylaluminum were collected, and unexpected structural features were observed, hinting toward yet unnoticed polarization effects. To approach these, a multipole refinement using the Hansen and Coppens method, followed by a topological analysis using Bader's quantum theory of atoms in molecules, was employed. The electron localization function based on density functional theory calculations supported the experimental findings. Thereby, unobserved electron shifts within the isobutyl group become detectable. It is shown that the impact of this electron shift is dependent mainly on whether the Bu-i substituent of the homoleptic triisobutylaluminum dimer [AI(i)Bu(3)](2)(1) is connected by a directional (sigma) or a multicenter (mu) bond to the metal. The effect found is assumed not only to be of paramount importance for organoaluminum compounds, widely used in synthesis and in the industrial value chain, but also to be present in organometallic chemistry in general.