Methods of fabricating one-dimensional composite nanofiber on a template membrane with porous array by chemical or physical process are disclosed. The whole procedures are established under a base concept of "secondary template". First of all, tubular first nanofibers are grown up in the pores of the template membrane. Next, by using the hollow first nanofibers as the secondary templates, second nanofibers are produced therein. Finally, the template membrane is removed to obtain composite nanofibers. Showing superior performance in weight energy density, current discharge efficiency and irreversible capacity, the composite nanofibers are applied to extensive scopes like thin-film battery, hydrogen storage, molecular sieving, biosensor and catalyst support in addition to applications in lithium batteries.