Alkyl- and phenylbis(dimethylamido)gallium, [RGa(NMe2)(2)](2) [R = Me (1), Et (2), Bu-n (3), (n)Hx (4), and Ph (5)], were synthesized by reactions of LiNMe2 with (RGaCl2)(2). The crystal structure of compound 1 was a disordered mixture of anti and syn isomers, with the ratio of anti/syn being 64:36, which was consistent with the ratio (57:43) found in the H-1 NMR spectrum. The Ga2N2 cores of the anti and syn structures were nonplanar. H-1 NMR spectra indicated the presence of both anti and syn isomers for all of the other substituents. H-1 NMR and mass spectra indicated that a species with the general formula of R3Ga2(NMe2)(3) was formed when these compounds were heated at high temperatures.