A porous polyvinylidene fluoride (PVDF) hollow nanofiber membrane was prepared by using coaxial electrospinning technology, and by adding dopamine (DA) to the inner core spinning solution, DA was insitu polymerized to form polydopamine (PDA) during the immobilization process, therefore laccase and horseradish peroxidase were fixed in the inner cavity of PVD hollow nanofibers. By optimizing the coaxial electrospinning parameters, the influence of the solvent ratio of the PVDF good solution and poor solution in the shell spinning solution, spinning temperature, and drying conditions on the structure of the PVDF hollow nanofiber membrane carrier was discussed. The surface hydrophilicity/hydrophobicity of the nanofibers, the catalytic activity and stability of the enzyme, and the influence of the structure on the performance of the immobilized enzyme were analyzed. The results show that the activity of the immobilized enzyme maintained 80% that of the free enzyme; after 7 days of storage, the activity of the immobilized enzyme was still 82% of the original activity; after 10 reaction operations, it still maintained more than 40% of its original activity. The porous PVDF hollow nanofiber membrane prepared by the coaxial electrospinning method is an excellent carrier for enzyme immobilization.