Reactive carbon capture (RCC) from bicarbonate solutions offers a highly efficient pathway for carbon-neutral fuel production by bypassing energy-intensive CO₂ desorption steps. However, conventional carbon paper (CP)-based electrodes suffer from electrolyte flooding and limited mass transport in liquid-fed RCC systems, impeding in-situ CO₂ regeneration from bicarbonate. Here, we report a hierarchical nickel foam (NF) electrode incorporating an asymmetric binder strategy that incorporates hydrophobic polytetrafluoroethylene (PTFE) in the microporous layer (MPL) and proton-conducting Nafion in the catalyst layer (CL). The macroporosity of NF and asymmetric binder architecture decouples bulk electrolyte transport from interfacial CO₂ regeneration. Operando Raman spectroscopy reveals that this asymmetric architecture effectively mitigates flooding and prevents excessive interfacial alkalization, facilitating rapid in-situ CO₂ regeneration from bicarbonate and ensuring a solid-liquid-gas three-phase boundary (TPB). Implemented in a bipolar membrane (BPM)-based membrane electrode assembly (MEA)-type electrolyzer, the NF electrode achieves a CO Faradaic efficiency (FE) of 62.6% at 100 mA/cm², operating at a low cell voltage of 3.26 V. Furthermore, the electrode exhibits robust durability, sustaining stable continuous operation for over 44 h. This structural engineering approach offers an effective and scalable strategy for overcoming mass transport limitations in RCC systems.