Caffeic acid (CA) is one of the phenolic compounds widely found in wines and it is associated to the quality of this beverage and also to various beneficial effects on health. Thus, a novel electrochemical sensor based on molecularly imprinted siloxanes (MIS) film was developed for the highly selective determination of CA. The MIS film was prepared by sol-gel process, using the acid catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS) and 3-aminopropyltrimethoxysilane (3-APTMS) in presence of CA as template molecule. The MIS film was immobilized onto Au electrode surface pre-modified with 3-mercaptopropyltrimethoxysilane (3-MPTS) and then characterized by Differential Pulse Voltammetry (DPV), Field Emission Scanning Electron Micrographs (FESEM) and Cross Polarization-Magic Angle Spinning Nuclear Magnetic Resonance of 29Si (29Si CP-MAS NMR). 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