Preferential CO oxidation (CO-PROX) is a promising approach for removing trace CO from hydrogen-rich streams, effectively preventing Pt anode poisoning in proton-exchange membrane fuel cells (PEMFCs). To effectively eliminate CO within the PEMFC operating temperature range, catalysts must exhibit high CO conversion and O2 selectivity. Expanding the operating temperature window of these catalysts is crucial. This study presents the synthesis of a CuCoCe ternary catalyst (CuCo/Ce-P) using an imidazole-functionalized porous organic polymer as a sacrificial template. Compared to the CuCoCe ternary catalyst prepared without a template (CuCo/Ce), CuCo/Ce-P exhibits significantly enhanced catalytic activity, with a T50 reduction from 85 °C to 55 °C and an expanded operating temperature window of approximately 40 ℃. Characterization results indicate that the imidazole-functionalized porous organic polymer facilitates improved dispersion of active species by anchoring metal ions through electron-rich groups, enhances intermetallic interactions, promotes electron transfer, and significantly improves the oxygen-deficient capacity of the CuCoCe ternary catalyst. Consequently, the catalyst exhibits a greater number of active interfaces, leading to enhanced catalytic activity and a wider operating temperature window.