In this work, we identify surface heating in the presence of molecular films as an alternative to bulk heating in electrocatalysis. We used the change in open circuit voltage of ferri/ferrocyanide to show that we are able to maintain relatively cooled bulk temperatures, even with heated electrode surfaces. Furthermore, we show that the high convection in the HT-ANEC cell affects the electrokinetics observed, supporting the fact that macroscopic forces are able to directly affect the catalyst microenvironment. With CO2 reduction, we show that without additive films, SH enhances activity, but only marginally alters selectivity. Upon the incorporation of an organic film, we demonstrate improved catalytic performance and shifting onset potentials that are consistent with values suggested by the temperature-dependent Butler-Volmer equation. Bayesian analysis of 40 electrolysis experiments at different potentials and temperatures enables identification of a reaction barrier with a probability distribution centered around 1.0 eV for the rate determining step for C2+ product formation, with elevated temperature also providing a decrease in overpotential of ca. 2 mV/K. The benefits of electrode heating are observed up to 60 °C, above which other effects, such as surface reconstruction and delamination of the organic film, may disrupt the activity vs. temperature trend. Collectively, the results illustrate the importance of holistic parameter estimation to establish models that guide the optimization of electrocatalytic systems.