Strategy that can design powerful photothermal‐catalysts to achieve photothermal‐effect assisted coupling‐catalysis is much desired for the improvement of energy conversion efficiency and redox product value in CO2 electroreduction system. Herein, a kind of bifunctional viologen‐containing covalent organic framework (Ni‐2CBpy2+‐COF) has been prepared and successfully applied in photothermal‐assisted co‐electrolysis of CO2 and methanol. Specifically, the FECO (cathode) and FEHCOOH (anode) for Ni‐2CBpy2+‐COF can reach up to ≈100 % at 1.9 V with ≈31.5 % saved overall electricity‐consumption when the anodic oxygen evolution reaction (OER) is replaced by methanol oxidation. The superior performance could be attributed to the cyclic diquats in Ni‐2CBpy2+‐COF that enhance the photothermal effect (ΔT=49.1 °C) to accelerate faster charge transfer between catalyst and immediate species as well as higher selectivity towards desired products as revealed by DFT calculations and characterizations. A kind of bifunctional viologen‐containing covalent‐organic‐framework has been prepared and successfully applied in photothermal‐assisted co‐electrolysis of CO2 and methanol. The superior performance could be attributed to the cyclic diquats in Ni‐2CBpy2+‐COF that enhance the photothermal effect to accelerate faster charge‐transfer between catalyst and immediate species as well as higher selectivity towards desired products.