Porous Ionic Liquids (PILs) have gained attention but facing challenges in catalysis, especially in liquid-liquid two-phase reactions due to limited catalytic sites and hydrophilicity control. This work engineered a Type III PILs (PILS-M) using zeolitic imidazolate framework-8 (ZIF-8) confined phosphomolybdic acid (HPMo) as the microporous framework and N-butyl pyridine bis(trifluoromethane sulfonyl) imide ionic liquid ([Bpy][NTf]) as the solvent. The PILS-M not only combines the advantages of traditional ionic liquids and microporous frameworks, including excellent extraction, high dispersion of catalytically active species, remarkable stability, etc., but also can make the inner surface of ZIF-8 turned to be hydrophilic that favors the contact between aqueous hydrogen peroxide oxidant and catalytically active sites for the promotion of catalytic performance in reactive extractive desulfurization (REDS) processes of fuel oils. This study demonstrates Type III PILs' potential as catalysts for sustainable chemical processes, offering insights into versatile PILs applications in diverse fields.