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This Perspective illustrates how the presence of internal and external electric fields can affect catalytic activity and selectivity, with a focus on heterogeneous catalysts. Specifically, experimental investigations of the electric field influence on catalyst selectivity in pulsed field mass desorption microscopes, scanning tunneling microscopes, probe–bed–probe reactors, continuous-circuit reactors, and capacitor reactors are described. Through these examples, we show how the electric field, whether externally applied or intrinsically present, can affect the behavior of a wide number of materials relevant to catalysis. We review some of the theoretical methods that have been used to elucidate the influence of external electric fields on catalytic reactions, as well as the application of such methods to selective methane activation. In doing so, we illustrate the breadth of possibilities in field-assisted catalysis.