Chemical vapor deposition methodologies are widely employed in a variety of fields such as microelectronics and glazing. Control of film growth and microstructure, and hence film properties, may be limited by precursor properties such as volatility or decomposition chemistry. In this paper we report how the incorporation of an applied electric field to aerosol assisted chemical vapor deposition reactions of vanadyl acetylacetonate in alcohols can influence the microstructure and growth of thin films of vanadium dioxide in unusual and sometimes unexpected ways. The films were characterized using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3519870] All rights reserved.