Step-and-pools are dominant morphologic traits of high-energy streams, where climatically- and biogeochemically-relevant gases are processed, transported to downstream ecosystems or released into the atmosphere. Yet, capturing the signature of the small-scale morphological complexity of channel forms on large-scale river outgassing represents a fundamental unresolved challenge. Here, we combine theoretical and experimental approaches to assess the contribution of localized steps to the gas evasion from river networks. The framework was applied to a representative, 1 km-long mountain reach in Italy, where carbon dioxide concentration drops across several steps and a reference segment without steps were measured under different hydrologic conditions. Our results indicate that local steps lead the reach-scale outgassing, especially for high and low discharges. These findings suggest that step-pools are key missing components of existing scaling laws used for the assessment of gas fluxes across water-air interfaces. Therefore, global evasion from rivers may differ substantially from previously reported estimates.