Catalyst development is needed to enable the use of renewable electricity to chemically convert carbon dioxide (CO2) and water into fuels and chemicals, a more sustainable, lower-carbon alternative to conventional processes that produce fuels and chemicals based on fossil resources. In this study, the catalytic activity and selectivity of polycrystalline platinum (Pt) is thoroughly characterized for the CO2 reduction reaction, based on an electrochemical cell design that offers high sensitivity for product detection. Thin polyaniline films are then electrodeposited onto polycrystalline Pt foils to form hybrid organic–inorganic surfaces. The addition of the polymer is observed to have an impact on the catalytic chemistry, yielding up to a fivefold enhancement in formate and CO production over pure Pt foils. This work elucidates new strategies to perturb interfacial chemistry in a manner that could help steer CO2 electro-reduction catalysis in desired directions.