In this work, a novel Co3O4@CeO2 nanofibrous membrane was prepared by the combination of interfacial defect engineering strategy and coaxial electrospinning for unusual levofloxacin degradation. Implanting active Co3O4 into CeO2 derived from Ce-UiO-66 created more oxygen vacancies and improved the interfacial interaction (electron transfer and specific surface area). In addition, accelerated redox recycling occurred on the catalyst surface because of the cooperation of Co sites and Ce sites. As a result, the optimal Co3O4@CeO2 nanocomposite showed an unexpectedly improved degradation efficiency of levofloxacin with a rate constant higher than 6.9 times (CeO2) and 2.6 times (Co3O4), superior elimination (>98%) of antibiotic (norfloxacin, tetracycline and doxycycline hydrochloride) and dyes (methylene blue, rhodamine b, methyl orange and crystal violet). Moreover, C-type hollow structure nanofibers with increased reaction area were prepared by coaxial electrospinning to support nanoparticles for consecutive wastewater treatment. The prepared nanofibrous membrane with loading 50 wt% Co3O4@CeO2 (PC50 NFMs) exhibited loose structure, resulting in 168.2 +/- 12 L m(-2) h(-1) of permeability driven by gravity, while 164.2 L m(-2) of levofloxacin was efficiently treated. Besides, the PC50 NFMs had satisfactory reusability and stability in real water bodies. This work paved a new avenue to control water pollution through the design of membranous catalysts.