We synthesized BDP-TFP-COF as one of the first examples for a porous material that incorporates BODIPY moieties within the structural backbone of a crystalline 2D COF. This direct approach avoids post-synthetic incorporation, which typically reduces both crystallinity and porosity. Instead, the eclipsed AA stacking and high crystallinity in BDP-TFP-COF provide large-scale domains of mesoporous channels for a facile introduction and uptake of molecular guests. The characterization of BDP-TFP-COF revealed high crystallinity, large surface area, and both chemical and thermal robustness combined with broad light absorption in the visible region. The combination of fluorinated mesopores and photosensitizing units in the backbone makes BDP-TFP-COF ideal for numerous applications. For instance, high adsorption capacity and water removal for BPA and MB showcases the potential for water remediation. In addition, ppb amounts of MB were detected in H2O via fluorescence quenching of colloidal BDP-TFP-COF suspensions. On the contrary, fluorescence enhancement was observed after selective deprotonation of the β-ketoenamine linkages with NEt3. This dual behavior of BDP-TFP-COF highlights the potential for selective sensing applications.