Electrooxidative polymerization of 3-ethylpyrrole on gold electrodes modified with spontaneously adsorbed monolayers (SAMs) of alkanethiols bearing 3-substituted pyrroles such as 3-(11-mercaptoundecyl)pyrrole, 4-(3-pyrrolyl)butyl 11-mercaptoundecanoate, and 11-mercaptoundecyl 3-pyrrolylacetate affords dense, robust, and extremely adhesive films of poly(3-ethylpyrrole). In the absence of monomer in contacting solution, the surface-confined monolayers are subject to irreversible electrooxidation. Scanning electron microscopy indicates that the presence of these monolayers enhances the morphological packing in films of poly(3-ethylpyrrole) compared to that of films deposited on unmodified electrodes. The conductivity of these films is enhanced as a consequence of this change in morphology.