Catalytically reactive membranes enable continuous and high yield chemical reactions while obviating the need for catalyst separation from the product stream. Despite recent advances, there still exists considerable challenges in developing high performance catalytic membranes. Most works to date have used planar membranes made of chemically inert materials, limiting conversion efficiency due to their low specific surface area and difficulty associated with incorporating a high density of catalytic nanoparticles on their surface. To overcome these limitations, we employ a single-step solvent transfer-induced phase separation (STRIPS) method to prepare nanocomposite hollow fiber membranes. Taking advantage of a dense layer of silica nanoparticles (NPs) on the surface of the STRIPS membrane, catalytic activity is imbued by coating the membrane surface with palladium (Pd)-supported metal-phenolic network (MPN). These catalytic hollow fiber membranes are used to perform Suzuki-Miyaura cross-coupling reactions, enabling continuous production of biaryl compounds with a high conversion efficiency (>90%) while retaining high permeability (>60 L/m2⋅h (LMH) at 1 bar-pressurized condition). The approach presented in this work synergistically combines hollow fiber nanocomposite structures and MPN coating to offer a versatile platform for developing the next generation reactive membranes for synthesizing valuable chemicals.