Dimeric [Ti(OiPr)2(benzaldoximate)2]2 was obtained upon reaction of titanium isopropoxide with two molar equivalents of benzaldehyde (E)- or (Z)-oxime or m-anisaldoxime. Two isomers were formed differing by the mutual orientation of the oximate ligands. Reaction with perillaldoxime or trans-cinnamaldoxime resulted in the corresponding derivatives with functional ligands. The degree of substitution was higher when o- or p-anisaldoxime were employed in the same molar ratio, and dimeric Ti2(OiPr)3(o-anisaldoximate)5 with a bridging oximate ligand and monomeric Ti(oximate)4 (oximate = o-anisaldoximate or p-anisaldoximate) were obtained. Dissolution of the p-anisaldoximate derivative upon heating in [D6]DMSO led to deoximation reactions.