Membrane capacitive deionization is considered as a promising technology for water treatment with their high efficiency, low capital cost, and environmental friendliness. However, the complex fabrication process of membrane capacitive deionization electrodes mainly hinders its viability in large-scale applications. In this study, a facile and general method to prepare free-standing electrodes for membrane capacitive deionization with an excellent electrosorption performance is presented. Electrospun nanofibers enclosing zinc-based nanoparticles are fabricated as the templates. After pyrolysis, the nitrogen-doped carbon nanofiber hybrids with high conductivity and a high surface area can be obtained readily. The carbon electrode material is able to achieve a salt adsorption capacity of 43.3 mg g(-1) at 1.4 V in 1000 mg L-1 NaCl aqueous solution. Overall, the carbon nanofiber hybrids electrode prepared by electrospinning and pyrolysis shows a great potential in membrane capacitive deionization for industrial applications.