The invention relates to a ferrous-manganese combined metal oxide magnetic nanofiber with a pipe-in-pipe structure and a preparation method of the ferrous-manganese combined metal oxide magnetic nanofiber. The nanofiber comprises manganous ferrite and manganese sesquioxide. The preparation method comprises the following steps: at first, preparing a spinning solution from polyvinylpyrrolidone (PVP), ferric salt, manganous salt and N,N-dimethylformamide (DMF), then preparing a composite fiber through an electrostatic spinning technology, and at last, calcining segment by segment to obtain the combined metal oxide magnetic nanofiber with the pipe-in-pipe structure. According to the combined metal oxide magnetic nanofiber and the preparation method, the technical route is simple, the operation is easy, the preparation process can be controlled relatively simply and conveniently, the raw materials are low in price, and wide in source, and the suitability for large-scale production is realized; through the adoption of a technology of calcining segment by segment, a nanofiber product, of which the appearance and the size are uniform, with the pipe-in-pipe structure can be obtained, the sample has certain magnetism, and can be independently applied to or compounded with other materials to be applied to the fields of sewage treatment and catalysis.