Eight new dimethylgallium complexes bearing 4-alkyl-2,6-bis(aryliminomethylene)-phenol ligands of type Me 2 GaL [L=4-methyl-2,6-bis-(phenyliminomethylene)-phenolato (3); L=4-methyl-2,6-bis-(p-methylphenyliminomethylene)-phenolato (4); L=4-methyl-2,6-bis-(1-naphthyliminomethylene)-phenolato (5); L=4-methyl-2,6-bis-(2-chlorophenyliminomethylene)-phenolato (6); 4-tert-butyl-2,6-bis-(phenyliminomethylene)-phenolato (7); L=4-tert-butyl-2,6-bis-(p-methylphenyliminomethylene)-phenolato (8); L=4-tert-butyl-2,6-bis-(1-naphthyliminomethylene)-phenolato (9); and L=4-tert-butyl-2,6-bis-(2-chlorophenyliminomethylene)-phenolato] (3) have been synthesized by the reaction of trimethylgallium with appropriate phenol. The complexes obtained have been characterized by elemental analysis, 1 H NMR, IR and mass spectroscopy, respectively. The solid-state structures of dimethyl[4-methyl-2,6-bis-(p-methylphenyliminomethylene)-phenolato]gallium (4) have been determined by X-ray single crystal analysis. In the structure, Ga atom is coordinated by one nitrogen atom and the other nitrogen atom remains constant. The distorted tetrahedron geometry around gallium is presented.