Six new molecular GaCl3 adducts of electron rich compounds of the carbone (carbodiphosphorane, tetraaminoallene) and cyclic alkyl amino carbene (CAAC) families have been synthesized and characterized by X-ray crystallography. The sum of their Cl-Ga-Cl angles has been compared to those of 20 other complexes exhibiting various oxygen-, nitrogen-, phosphorus-, and carbon-donor ligands for which good quality X-ray analyses have been reported. The pyramidalization of the GaCl3 moiety in L center dot GaCl3 complexes has been checked against the computed antisymmetric stretching of the Ga-Cl bonds. It has also been compared to the symmetric stretching of the C-O bonds of the corresponding L center dot Ni(CO)(3) complexes (Tolman Electronic Parameter). On this basis, a relationship between the pyramidalization observed in the gallium complexes and the electronic ligand properties has been established.