Carbon dioxide (CO2) utilization as C1 feedstock under metal/co-catalyst-free conditions facilitates the development of eco-friendly routes for mitigating atmospheric CO2 concentration and producing value-added compounds. In this regard, herein, we designed a bifunctional porous organic polymer (POP-1) by incorporating acidic (-CONH) and CO2-philic (-NH/N) sites by judicious choice of organic precursors. Indeed, POP-1 exhibits high heat of interaction for CO2 (40.2 kJ/mol) and excellent catalytic performance for transforming carbon dioxide to cyclic carbonates, a high-value commodity chemical with high selectivity and yield under metal/cocatalyst/solvent-free atmospheric pressure conditions. Interestingly, an analogous polymer (POP-2) that lacks basic (-NH/N) sites showed lower CO2 interaction energy (31.6 kJ/mol) and catalytic activity than that of POP-1. The theoretical studies further supported the superior catalytic activity of POP-1 in the absence of Lewis acidic metal and cocatalyst. Notably, POP-1 showed excellent reusability with retention of catalytic performance for multiple cycles of usage. Overall, this work presents a novel approach to metal/cocatalyst/solvent-free utilization of CO2 under eco-friendly atmospheric pressure conditions.