A novel architecture of nickel current collector (NCC) is fabricated cost-effectively by electrospinning. An ultrathin MnO₂ coating is electrodeposited on to the NCC and the resultant nano-networks of MnO₂ shell/NCC core are used as supercapacitor electrodes. Excellent electrochemical performance is revealed at a high charge/discharge rate. The cyclic voltammetry measurements show that the current is stable even at a scan rate as fast as 200 mV s⁻¹. A capacitance of 214 F g⁻¹ is obtained by galvanostatic testing at a current density as large as 20 A g⁻¹, which is much higher than that of MnO₂ coated Ni foam.