Spherical and rod shaped organic-capped TiO2 nanocrystals (NCs), prepared by a hydrolytic route, were deposited as thin films and characterized by means of atomic force microscopy (AFM), X-ray diffraction (XRD) and surface plasmon resonance (SPR). SPR was assessed as transduction technique in order to test the sensing ability of the prepared films for detection of alcohol vapours as a function of NC shape and thermal treatment. The performances of the TiO2 nanocrystals were found to be dependent on the titania nanocrystal morphology and thermal treatment conditions, pointing to the beneficial effect of a rod-like shape as compared to a spherical one, and to a possible role of the titania surface organic coating in enhancing the sensor response.