Atomically dispersed Co–N–C coordination is a promising strategy for providing acidic activity sites for catalytic amine solvent regeneration, but the control of the coordination environment remains a major challenge. Herein, the sulfo group (-SO3H) introduced to improve the Co–N–C coordination and morphology of COF supports. The new coordination configuration (Co–N/C/O) significantly increased the acidic activity of the COF catalysts with single-atom Co and promote the surface areas (696 m2/g). The sulfonic-coordinated Co–N–C (S–Co/NC) catalysts exhibited superior spent solvent regeneration activity at lower concentrations compared with previously described catalysts. Moreover, the maximum desorption rate (3.74 CO2 mmol/min) considerably increased by 733% compared with the catalyst-free reaction, resulting in approximately 39% lower relative heat duty. This study presented an efficient and feasible method for atomic-level tuning of the Co–N–C catalyst for developing excellent solid acid catalysts for energy-efficient amine solvent regeneration.