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Practical CO₂ and CO electroreduction are often operated at elevated temperatures, yet the correlation between the temperature increase and catalytic activity and selectivity has not been well-defined. This study uncovers that higher temperatures enhance *CO coverages, but in CO₂ reduction, they also promote *CO desorption to vapor-phase CO, lowering C₂H₄ selectivity. In CO reduction, elevated temperatures facilitate CO diffusion to overcome the unfavorable *CO adsorption thermodynamics, which promotes C—C coupling. More details are discussed in the article by Wang et al. on pages 2705—2711.