Compounds of the type [(Bu(t))(2)Ga(mu-OR)](2), where R = Me (1), Et (2), Pr-n (3), Pr-i (4), Bu(n) (5), Bu(i) (6), Bu(s) (7), Bu(i) (8), n-C5H11 (9), CH2CH2Pri (10), C(H)Et(2) (11), CH(2)Bu(t) (12), n-C6H13 (13), cyclo-C6H13 (14), Ph (15), CH(2)Ph (16), have been synthesized and characterized by H-1 and C-13 NMR and IR spectroscopy, and mass spectrometry. All the compounds are dimeric. The molecular structure of compounds 1, 3, 9, 11, 12, 13 and 15 have been determined by X-ray crystallography. The geometry of the Ga2O2 core is found to be independent of the substituents at oxygen, but steric interactions with the gallium-tert-butyl groups do modify the conformation adopted by the alkoxide group. The crystal packing of [(Bu(t))(2)Ga(mu-OR)](2) for substituents with carbon chains of five or lower is dependent on the packing of the organometallic [(Bu(t))(2)Ga(mu-O)(2)Ga(Bu(t))(2)] core, while for longer carbon chains the amphiphilic inter-molecular interactions dominate the packing