Homoleptic gallium tris(alkoxides) [Ga(OR)₃]₂ were prepared by the reaction of [Ga(NMe₂)₃]₂ (1) and excess ROH (R = CH₂CH₂NMe₂ (2), CH(CH₃)CH₂NMe₂ (3), C(CH₃)₂CH₂OMe (4), CH₂CH₂OMe (5)) in toluene at room temperature. Compounds 2–5 were isolated as colourless oils. The side-products, [Ga(OCH₂CH₂NMe₂)₂Cl] (6), [Ga(OCH(CH₃)CH₂NMe₂)₂Cl] (7) and [Ga(OC(CH₃)₂CH₂OMe)Cl₂]₂ (8) were also isolated in low yield during the synthesis of 2, 3 and 4, respectively. However, compounds 6 and 7 were also prepared directly from the reaction of [Ga(NMe₂)₂Cl] and 2 equivalents of ROH (6, R = CH₂CH₂NMe₂; 7, R = CH(CH₃)CH₂NMe₂). Similarly, compound 8 was isolated from the reaction of [Ga(NMe₂)Cl₂] and 1 equivalent of HOC(CH₃)₂CH₂OMe. Single crystal X-ray crystallography showed that the gallium bis(alkoxides) (6 and 7) are monomeric in the solid state with the gallium centre adopting a distorted trigonal bipyramidal geometry. In contrast, the gallium mono(alkoxide) 8 is dimeric.