A diverse series of aluminum chloride alkoxides, [ClxAl(mu-OR)(y)](n) (R = Bu-n, (c)Hex, Ph, 2,4-(Bu2C6H3)-Bu-t), was synthesized using the reactions of dichlorethylalane (EtAlCl2) with cyclohexanol ((c)HexOH), n-butanol ((BuOH)-Bu-n), and phenols (PhOH and 2,4-(Bu2C6H3OH)-Bu-t). Eight molecular products were isolated and structurally characterized. The dimedc [Cl2Al(mu-O(c)Hex)(2)AlCl2] (1) was the smallest oligomer isolated among the cyclohexanolate derivatives. The adduct of 1 with cyclohexanol is a dinuclear molecule [Cl-2(HO(c)Hex)Al(mu-O(c)Hex)(2)AlCl2] (2) which represents a possible intermediate in the conversion reaction leading to the formation of a trinuclear bicyclic [ClAl{(mu-O(c)Hex)(2)AlCl2}(2)] (3). Two polymorphic forms of 3 were isolated. Further coordination of cyclohexanol to the Lewis acidic five-coordinate aluminum atom in 3 provided [Cl-2(HO(c)Hex)Al(mu-O(c)Hex)(2)AlCl2] (4) with octahedrally coordinated central aluminum. Compound 4 could be regarded as a precursor to the well-known Mitsubishi (tridiamond) tetranuclear species. The reactions of EtAlCl2 with less sterically demanding (BuOH)-Bu-n yielded a cyclic trimer, [Cl2Al(mu-(OBu)-Bu-n)](3) (5), and a unique trinuclear ionic species, [Cl2Al{(mu-OH)(mu-(OBu)-Bu-n)AlCl((HOBu)-Bu-n)(3)}(2)]Cl (6) with a linear Al(mu-o)(2)Al(mu-O)(2)Al core. In the reactions with phenols, the aromatic groups preferentially stabilized dimeric structures of [Cl2Al(mu-OR)(2)AlCl2] (R = Ph, 7; 2,4-(Bu2C6H3)-Bu-t, 8). Since these compounds could be considered as intermediates in the nonhydrolytic condensation reactions of metal halides with metal alkoxides, a mixture of EtAlCl2 with (c)HexOH was used as a precursor for the nonaqueous synthesis of alumina by alkylhalide elimination.