Inspired by dative boron‐nitrogen (B←N) bonds proven to be the promising dynamic linkage for the construction of crystalline covalent organic polymers/frameworks (COPs/COFs), we employed 1,4‐bis(benzodioxaborole) benzene (BACT) and N,N'‐Di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxdiimide (DPNTCDI) as the corresponding building blocks to construct a functional COP (named as CityU‐25), which had been employed as an anode in rechargeable lithium ion batteries. CityU‐25 displayed an excellent reversible lithium storage capability of 455 mAh/g after 170 cycles at 0.1 A/g, and an impressive one of 673 mAh/g after 720 cycles at 0.5 A/g. These findings suggest that CityU‐25 is a standout candidate for advanced battery technologies, highlighting the potential application of this type of materials