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2-Methoxyalkanols exhibit interesting variations with regard to equilibrium species of non hydrogen bonded, intramolecular hydrogen bonded and intermolecular hydrogen bonded forms [1-9]. 2-Methoxyethanol in particular has been found to behave as an anion as well as a bidentate ligand in its metal complexes [10-14], Trimethylsiloxyalkanols, Me3SiO(CH2)nOH synthesized through a simple way, are a new class of potentially bidentate ligands with different basicity of the oxygen atom and steric conditions. In the present paper, the synthesis and nature of trimethylsiloxyalkanols is described.