In this study, a polypyrrole/nickel (PPy/Ni) nanocomposite has been synthesized through an in situ polymerization method. X-ray diffraction, Raman spectroscopy and Fourier transform infrared spectrometer confirm the formation of PPy in the PPy/Ni nanocomposite. From the scanning and transmission electron microscopy images, one can see that the nickel nanoparticles, which are approximately 21nm, are encapsulated in the PPy nanofibres. Cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy are used to test the electrochemical performance of the PPy/Ni electrode. The specific capacitance of the PPy/Ni is approximately 488Fg−1 at a current density of 250mAg−1, which is superior to that of pure PPy (408Fg−1) and also demonstrates good cyclability and low charge-transfer resistance.