Fluorinated porous organic networks (F-PONs) have demonstrated unique properties and applications, but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported. Herein, using polydivinylbenzene (PDVB) as an easily available precursor, a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Brønsted acid (trifluoromethanesulfonic acid). The afforded material (F-PDVB) featured high fluorine content (22 at.%), large surface area (771 m²·g^-1), and good chemical/thermal stability, rendering them as promising candidates for the adsorption of CO₂, hydrocarbons, fluorocarbons, and chlorofluorocarbons, with weight capacities up to 520 wt.% being achieved. This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers (F-HCPs) from rigid aromatic monomers. The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.