Metal sulfides have aroused great interest for energy storage. However, their low specific capacities and inferior rate capabilities hinder their practical applications. In this work, a facile cobalt-doping process is used to boost the electrochemical performance of Ni@Ni S core-sheath nanowire film electrodes for high-performance electrochemical energy storage. Co ions are doped successfully and uniformly into Ni S nanosheets through a facile ion-exchange process. The electrochemical properties of film electrodes are improved greatly, and an ultrahigh volumetric capacity (increased from 105 to 730 C cm at 0.25 A cm ) and excellent rate capability are obtained after Co is doped into Ni@Ni S core-sheath nanowires. A hybrid asymmetric supercapacitor with Co-doped Ni@Ni S as the positive electrode and graphene-carbon nanotubes as the negative electrode is assembled and exhibits an ultrahigh volumetric capacitance of 142 F cm (based on the total volume of both electrodes) at 0.5 A cm and excellent cycling stability (only 3 % capacitance decrease after 5000 cycles). Moreover, the volumetric energy density can reach 44.5 mWh cm , which is much larger than those of thin-film lithium batteries (1-10 mWh cm ). These results may provide useful insights for the fabrication of high-performance film electrodes for energy-storage applications.