To try to solve the problem of delamination of polypyrrole from gold during electrochemical cycling, 1-(2-thioethyl)pyrrole and 3-(2-thioethyl)pyrrole were synthesized as adhesion promoters. These compounds were designed to bind to gold through the sulfur atom to form monolayers, and their alkyl chains were made short to permit electron transfer to and from the pyrrole moieties. It was hoped that during electropolymerization of unmodified pyrrole in solution, the pyrrole moieties of the monolayer would be incorporated into the growing film. In this first paper of the series, the synthesis and characterization of the monomers and their electrochemical polymerization to form thin films is presented. Nuclear magnetic resonance and infrared, Raman, US-vis-NIR, and mass spectroscopy measurements form a basis for comparison with monolayers adsorbed on gold surfaces in the following papers.