Covalent organic frameworks (COFs) have great potential for photocatalytic CO2 reduction, owing to their adjustable structures, porous characteristics, and highly ordered nature. However, poor light absorption, fast recombination of photogenerated electron-hole pairs, and suboptimal coordination conditions have contributed to the hindered efficiency and selectivity observed in photocatalytic CO2 reduction processes. In this work, the integration of bromine (Br) atoms into COFs was achieved through the synthesis process involving nickel (II) tetraaminophthalocyanine (NiTAPc) and 3,6-dibromopyromellitic dianhydride (BPMDA) using a solvothermal approach. The coupling of a porous framework structure alongside the incorporation of Br atoms yields a significant enhancement in photoelectric properties compared to bromine-free COFs. Meanwhile, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations revealed that the introduction of Br atoms can facilitate the adjustment of the electron configuration around the phthalocyanine unit and diminish the required energy for the photocatalytic reaction. When subjected to visible light irradiation, the NiTAPc-BPMDA COF showcased a CO yield of 148.25 μmol g-1 over a 5-hour period, accompanied by an impressive selectivity of 98%. This work highlights the collaborative influence of phthalocyanines and Br atoms within COF-based photocatalysts, offering an alternative approach for designing and constructing high-performance photocatalysts with elevated yield and selectivity. The synergistic role of phthalocyanines and Br atoms within the COF-based photocatalysts provides an alternative strategy for photocatalysts with high yield and selectivity in the future.