We explore dynamic electrocatalysis by pulsing the applied potential to modulate the temporal microenvironment during the electrochemical reduction of CO2. We focus on copper electrodes by virtue of their unique ability to bind *CO intermediates and enable C-C coupling to form high-value C2 products, such as ethylene or ethanol. We examine the well-known competition between *CO and *H for active sites, as their relative coverage is crucial for enhancing the formation of C2 products. We found that pulsing the applied potential can significantly enhance the electrocatalytic activity of C-C coupling, increasing the turnover frequency of C2 products by up to 33-fold compared to potentiostatic electrolysis. We interpret this improvement in the context of oscillating surface coverage and the transient dynamics of the *CO/*H coverage during the cathodic pulse. Through a combination of experimental and computational methods, we investigate how pulse frequency influences the turnover frequency of CO2 to C2 products on Cu. Our study not only validates recent theoretical predictions about the potential of dynamic (electro)catalysis to surpass the limitations imposed by the Sabatier limit but also uncovers scientific and mechanistic insights into dynamic processes within the electrical double layer. These insights are instrumental in formulating design principles for pulsed CO2 electrolysis with enhanced C2 activity. The outcomes of this study lay a foundational framework for future advances in programmable CO2 electrolysis with improved activity, selectivity, and durability. © 2024 American Chemical Society.