We present a systematic study on the effects of electropolymerization parameters of polypyrrole-dodecylbenzenesulfonate (PPy(DBS)) surfaces on the flattening behaviors of organic droplets during reduction and oxidation (redox). PPy(DBS) surfaces were fabricated under varying electropolymerization conditions, including voltage, surface charge density, and dopant electrolyte (DBS-) concentration. The flattening behaviors on different PPy(DBS) surfaces were characterized by analyzing droplet behaviors and energy-dispersive X-ray spectroscopy (EDS) data. The surface charge density and voltage during electropolymerization determined the thickness and doping ratio of synthesized PPy(DBS) surfaces, affecting how DBS- molecules are released from PPy(DBS) upon reduction. The release amount and rate of DBS- molecules were strongly related to the droplet flattening time.