Optically flat polymer films of poly(N-hexadecylpyrrole) (PHDPy) have been successfully prepared on gold electrodes modified with self-assembled monolayers of bis(ω-(N-pyrrolyl)-n-undecyl) disulfide (BPUS). During the growth of PHDPy, the surface-confined pyrroles in BPUS serve as nucleation sites for the epitaxial growth of PHDPy instead of being laterally polymerized to form polymeric monolayers. We provide visual evidence to confirm the chemical reaction between the surface-confined pyrroles and HDPy in the solution. Polymer growth on the modified and unmodified electrodes is investigated using cyclic voltammetry, optical microscopy, and scanning probe microscopy.