The development of advanced porous materials for effectively separating uranium from nuclear wastewater or seawater is a highly coveted yet formidable task. However, the importance of the covalent organic frameworks (COFs) skeletons and the specific arrangement of adjacent atoms is often disregarded when configuring coordination settings for chelating molecules. In this study, a novel material for oxygen-enriched COFs was developed. The optimized oxygen-rich COFs showed aligned neighboring bonds and triazine groups along the skeletons, resulting in an increase in uranyl binding sites and a threefold rise in the total number of binding sites. The synergistic interaction of ether bonds and triazine groups in the π-conjugated skeletons significantly reduced the energy band gap, leading to improved uranium affinity and recovery. The adsorption capacity reached an impressive 660 mg/g, surpassing that of most COF-based adsorbents using a chemical coordination mechanism in uranium-containing aqueous solutions. This study provides valuable insights into designing novel adsorbents for uranium separation.