Porous NiO-ZnO hybrid nanofibers were prepared by a single-nozzle electrospinning technique combined with subsequent heating treatment. The resultant nanofibers are composed of interconnected primary nanocrystals and numerous nanopores with heterostructures between NiO and ZnO. Such characteristics of the structure can lead to excellent electrochemical performances when the nanofiber was evaluated as an anode material for lithium-ion batteries. The porous NiO-ZnO nanofiber electrode delivers a high discharge capacity of 949 mA h g(-1) after 120 cycles at 0.2 A g(-1), and maintains around 707 mA h g(-1) at a current density as high as 3.2 A g(-1). Even after cycling at high rates, the electrode still retains a high discharge capacity of up to 1185 mA h g(-1) at 0.2 A g(-1).