A novel manganese dioxide (MnO2) nanosheet network grown on nickel/polyvinylidene fluoride (Ni/PVDF) coaxial fiber membrane is successfully fabricated by a three-step route: the polyvinylidene fluoride fiber membrane is prepared by electrospinning method, and then the Ni(shell)/PVDF(core) coaxial fiber membrane with core–shell structure can be obtained by the electroless deposition, and ﬁnally the manganese dioxide nanosheet network grown on Ni/PVDF coaxial fiber membrane can be achieved by using a simple hydrothermal treatment. This as-prepared binder-free and ﬂexible composite membrane is directly used as anode for lithium ion batteries. The excellent electrochemical performance of the composite membrane can be attributed to the unique combinative effects of nanosized MnO2 network and conductive Ni/PVDF fiber matrix as well as the porous structure of composite fiber membrane.