Advanced oxidation processes have extensive applications in the degradation of organic pollutants in wastewater. However, conventional powder photochemical catalysts have limited utility due to their susceptibility to agglomeration, electron-hole recombination, and challenges in recycling. In this work, we herein propose an integration tactic to facilely fabricate a cellulose-based photocatalytic electrospun membrane (ZPP/CA-ENM) via synchronous electrospinning of acetate cellulose (CA) and electrospray of core-shell PMMA@PDA@ZIF-67 (ZPP) photocatalysts. This hybrid membrane is capable of synergistic PMS activation and photocatalytic degradation of tetracycline (TC) and methylene blue (MB). For the ZPP catalysts, the PDA@ZIF-67 heterojunctions greatly promote the adsorption of visible light and the separation of photogenerated electron-hole pairs, leading to excellent catalytic efficiency. The synchronous electrospinning and electrospray not only lead to the formation of porous and spiderweb-like membrane structure, but also facilitates the dispersion and recycling of these catalysts. Results reveal that under the presence of light irradiation and PMS, various oxidative species, including 1O2, SO4−, OH and O2− are generated, resulting in rapid degradations of TC (93.31 % within 30 min) and MB (99.90 % within 15 min), which also exhibits a rapid degradation and high efficiency in a cascade continuous lab setup. This work provides a new strategy for exploring novel and efficient material for wastewater purification.