Abstract In this study, we present a novel approach for the synthesis of covalent organic frameworks (COFs) that overcomes the common limitations of non‐scalable solvothermal procedures. Our method allows for the room‐temperature and scalable synthesis of a highly fluorinated DFTAPB‐TFTA‐COF, which exhibits intrinsic hydrophobicity. We used DFT‐based calculations to elucidate the role of the fluorine atoms in enhancing the crystallinity of the material through corrugation effects, resulting in maximized interlayer interactions, as disclosed both from PXRD structural resolution and theoretical simulations. We further investigated the electrocatalytic properties of this material towards the oxygen reduction reaction (ORR). Our results show that the fluorinated COF produces hydrogen peroxide selectively with low overpotential (0.062 V) and high turnover frequency (0.0757 s −1 ) without the addition of any conductive additives. These values are among the best reported for non‐pyrolyzed and metal‐free electrocatalysts. Finally, we employed DFT‐based calculations to analyse the reaction mechanism, highlighting the crucial role of the fluorine atom in the active site assembly. Our findings shed light on the potential of fluorinated COFs as promising electrocatalysts for the ORR, as well as their potential applications in other fields.