This study presents a method to enhance the oxygen reduction reaction (ORR) activity of covalent organic frameworks (COFs) by modulating the electronic states of pyridine nitrogen atoms within their structures. The research focuses on the synthesis and characterization of three COF variants: PY-BPY-COF, ion-PY-BPY-COF, and im-PY-BPY-COF, each incorporating different pyridine units. The im-PY-BPY-COF, which includes ionic imidazole units, demonstrated the highest ORR activity, with a half-wave potential of 0.80 V in 0.1 M KOH, surpassing other metal-free COFs. The enhanced performance is attributed to the improved electronic conductivity of the im-PY-BPY-COF, which is 6.8 × 10⁻⁸ S cm⁻¹, significantly higher than that of the other COFs. Theoretical calculations and in situ synchrotron radiation Fourier transform infrared spectroscopy confirmed that the ionic imidazole rings facilitated the binding of the intermediate OOH* and promoted the desorption of OH*, thereby enhancing the catalytic activity. The study highlights the importance of tuning the electronic properties and functional groups of COFs to achieve high-performance ORR catalysts, offering new insights into the design of metal-like COF catalysts for efficient oxygen reduction reactions.This study presents a method to enhance the oxygen reduction reaction (ORR) activity of covalent organic frameworks (COFs) by modulating the electronic states of pyridine nitrogen atoms within their structures. The research focuses on the synthesis and characterization of three COF variants: PY-BPY-COF, ion-PY-BPY-COF, and im-PY-BPY-COF, each incorporating different pyridine units. The im-PY-BPY-COF, which includes ionic imidazole units, demonstrated the highest ORR activity, with a half-wave potential of 0.80 V in 0.1 M KOH, surpassing other metal-free COFs. The enhanced performance is attributed to the improved electronic conductivity of the im-PY-BPY-COF, which is 6.8 × 10⁻⁸ S cm⁻¹, significantly higher than that of the other COFs. Theoretical calculations and in situ synchrotron radiation Fourier transform infrared spectroscopy confirmed that the ionic imidazole rings facilitated the binding of the intermediate OOH* and promoted the desorption of OH*, thereby enhancing the catalytic activity. The study highlights the importance of tuning the electronic properties and functional groups of COFs to achieve high-performance ORR catalysts, offering new insights into the design of metal-like COF catalysts for efficient oxygen reduction reactions.