<p>Introducing an external photo field would effectively enhance electrocatalysis such as electrocatalytic CO₂ reduction reaction (CO₂RR), but suffer from the limited utilization efficiency of the photo-generated carriers. To address this challenge, herein, metal halide perovskite quantum dots (e.g., CsPbBr₃) with high light-absorption coefficients, were encapsulated into cobaltporphyrin- based covalent-organic frameworks (COFs) (COF-366-Co). The synthesized perovskite-COF composite material effectively improved the performance of the photocoupled electrochemical CO₂RR. The optimal CsPbBr₃@COF-2 exhibited a CO Faradaic efficiency of 93.4% at −0.7 V vs. reversible hydrogen electrode (RHE), and achieved a turnover frequency (TOF) of 3395.5 h⁻¹ at −0.9 V under visible light, all of which far exceeded the values recorded in the dark. The evidently higher performance is ascribed to the favorable interfacial charge transfer from CsPbBr₃ quantum dots to COF-366-Co, which effectively accelerates charge separation and then promotes the participation of photogenerated electrons in the CO₂ reduction reaction under photoelectric conditions. Additionally, the encapsulation of the CsPbBr₃ quantum dots in hydrophobic COF-366-Co can suppress undesired agglomeration and decomposition by providing a physical and chemical barrier in reaction systems containing water. Briefly, this work provides a new avenue to design high-performance photocoupled electrocatalytic materials via enhancing the interfacial electric field.</p>