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Hollow nitrogen (N)-doped Fe 3 O 4 /carbon (C) nanocages with hierarchical porosities have been successfully synthesized by carbonizing polydopamine (PDA)-coated Prussian blue (PB). Scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy and N 2 adsorption/desorption isotherms were employed to characterize the hollow N-doped Fe 3 O 4 /C superstructures. Owing to their well-defined hierarchical porous structure and high electric conductivity originated from N-doped carbon matrix, the unique hollow nanocages as anode materials for Lithium ion batteries (LIBs) exhibited a specific capacity of 878.7 mA h g −1 after 200 cycles at the specific current of 200 mA g −1 , which is much better than that of N-doped Fe 3 O 4 /C derived from pure PB (merely 547 mA h g −1 ). The novel construction with hollow interior nanoarchitecture, hierarchical porosity, high electrical conductivity, N-doped carbon, and the Fe 3 O 4 nanoparticles incorporated into porous interconnected carbon framework make the special nanocomposites be very promising Fe 3 O 4 -based anode materials. [ABSTRACT FROM AUTHOR]