Nanofiber has been widely used in numerous fields for its good advantages such as large surface area and porosity. However, the relationship between nanofiber structure and coaxial electrospinning process is still not clear and deserved to be studied. In this work, a kind of polyurethane/nickel ( PU/Ni ) nanofiber with core-shell structures was developed, and the effects of electrospinning parameters on the properties of nanofiber were evaluated. The results showed that the optimized parameters of core-shell electrospinning speeds were 1 mL/h ( core ) and 1 mL/h ( shell ) , respectively. Sample c with the core-shell electrospinning speed ratio of 1 : 1, exhibited the relatively smooth surface, good orientation, and bonding points. It also had the largest tensile strength at 99 cN, tensile elongation at 44.86％, and the best electricity conductivity, which showed great potential in the application of nanofiber fields.