The article discusses the potential of covalent organic frameworks (COFs) in photocatalytic water splitting for green hydrogen production. Despite the advantages of COFs in photocatalysis, challenges such as low efficiency and the need for expensive Pt co-catalysts persist. The article introduces a novel approach of utilizing ionic polarization through post-synthetic modification to enhance the performance of COFs. By endowing β-keto-enamine-based COFs with cationic frameworks via quaternization reaction, the efficiency of charge separation and migration is significantly improved, leading to enhanced dipole moment and lower exciton dissociation energy. The incorporation of counteracting iodide anions as electron-withdrawing groups promotes electron transfer and reduces the energy barrier for hydrogen formation. This strategy results in higher photocatalytic activities for water splitting, with the H2 evolution rate reaching 9.21 mmol g−1 h−1 without the need for Pt co-catalysts. The study showcases the potential of ionic polarization in COFs to revolutionize the field of photocatalysis, offering a sustainable and efficient approach for hydrogen production.