The reactions between Ti(OR)4 and allylacetatoacetate (HAAA) in 1:1 or 1:2 stoichiometry at rt gave Ti2(OR)6(AAA)2 R = Et (1), iPr (2) and Ti(OR)2(AAA)2 R = Et (3), iPr (4) species. A monosubstituted derivative Ti2(OiPr)6(AMP)2 (5) was isolated with allylmethylphenol (AMPH). 1 and 5 were characterized by single crystal X‐ray diffraction. Their molecular structures consist of dimers with the polymerizable ligands in terminal positions andbridging alkoxide ligands assembling five and six‐coordinated metal atoms, respectively. The Ti‐O bond lengths of 1 are in the range 1.76(1) to 2.11(1) Å with the variation Ti‐OEt < Ti‐μ‐OEt < Ti‐η2‐O (allylacetatoacetate). All compounds were characterized by FT‐IR and 1H NMR. The possibility to accede to more extended arrays either by hydrolysis or by radical initiated homo‐ or co‐polymerization reactions was investigated for the allylacetato derivatives as well as for Ti(OiPr)2(AAEMA)2 AAEMA = [2‐(methacryloyloxy)ethylacetoacetato] for the latter reactions.

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