This paper describes a general approach to rapid generation and screening of catalytic materials on electrode surfaces. The properties of the corresponding polymers, including catalytic performance, can be modulated by varying the monomer feed ratios, monomer concentrations, and applied polymerization potential, Thus, the generation of the polymeric TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy) catalysts was performed by electrochemical copolymerization of 2,2'-bithiophene with the TEMPO catalyst precursors containing pyrrole side chains. A library of catalyst films was obtained over a wide range of bithiophene/pyrrole ratios upon repeated scanning of the applied potential from +0.5 to +1.4 V (vs Ag/AgCl). The resulting catalyst films were utilized in both chemical and electrochemical oxidation of primary alcohols to aldehydes.