Perfluorooctanoic acid (PFOA) poses a substantial threat to human health due to its bioaccumulation and carcinogenic nature. Current remediation strategies typically focus on either adsorption or degradation, neglecting the potential of an integrated approach. Herein, we present a pyrazolate metal–organic framework (MOF), PCN-1003, featuring a lamellar structure with one-dimensional open channels. PCN-1003 exhibits exceptional stability across a wide pH range (1–12) in aqueous solutions, achieving efficient PFOA adsorption (642 mg g⁻¹). Mechanistic studies revealed that a PFOA–acetate exchange process dominates, representing a remarkable example of such a mechanism and enabling efficient PFOA uptake. Notably, PCN-1003 greatly facilitates PFOA degradation at a much lower temperature (90 °C) than observed in previously reported methods, with an approximately threefold catalytic acceleration effect, attributed to the coordination of PFOA and the confined environment within PCN-1003. This study pioneers integrated PFOA concentration and degradation using a single MOF, presenting a promising avenue for treating water contaminated with per- and polyfluoroalkyl substances.