Unique one dimensional ZnFe2O4 hollow fibers with integrated tubular mesoporous nanostructures have been fabricated successfully using a two-step process, combining the single-spinneret electrospinning and the simple post-treatment techniques. The original hollow fibers that were obtained from the single-spinneret electrospinning device consisted of a ZnFe2O4 shell and a carbonaceous inner fiber layer (fiber-in-tube structure). The unique integrated tubular nanostructure of the hollow fiber (tubular structure) was then achieved by removing the inner fiber layer using a hydraulic treatment process. A series of analyses were carried out to study the characteristics of the hollow fibers, such as morphologies, structures, crystalline phases, chemical compositions and pore properties. It was found that the ZnFe2O4 tubular structure exhibited a higher capacity of 1026mA h g−1 after 260 cycles at a current density of 200mAg−1 than the fiber-in-tube structure (711mAhg−1) under the same experimental conditions. However, the tubular structure suffered a larger capacity loss and longer capacity fading period in the first few cycles of the charge-discharge, indicating a weaker cycling stability compared with the fiber-in-tube structure. These differences in electrochemical performance during the charge-discharge processes were due to the diverse morphologies and nanostructures of the hollow fibers.