Here, the facile synthesis of four‐length‐scaled (ultramicro‐micro‐meso‐macroporous) hierarchically structured porous carbon nanocomposite by an emulsion‐template strategy is reported. This previously unreported combination of zeolite nanocrystals embedded in the walls of microcellular carbon foams gives unique textural and structural properties, which result in their excellent ability to selectively capture CO₂ owing to the presence of ultra‐micropores. The zeolite–microcellular carbon foam synergism delivers an adsorbent with a significantly enhanced CO₂ capture capacity of up to 5 mmol g⁻¹, CO₂/N₂ selectivity of up to 80, and an outstanding multi‐cycle capture performance under humid conditions (70 % performance retention after 30 regeneration cycles). More impressively, the electrically conductive carbon framework enables Joule heating and cooling, and thus fast and energy‐efficient regeneration is possible, with an estimated energy consumption of only about 12 kWh.