Manganese dioxide coated titanium dioxide (MnO₂-TiO₂) nanofibers, prepared by electrospinning and post-hydrothermal process exhibited high electrochemical properties in aqueous Na₂SO₄ electrolyte. The thin MnO₂ shell with average thickness of 10 nm contributed to the high electrochemical performance for charge storage by redox reaction and intercalation mechanisms, while the anatase phase TiO₂ core provided an easy pathway for electronic transport with additional electrochemical stability over thousands of charge-discharge cycles. An asymmetric supercapacitor designed from the MnO₂-TiO₂ nanofibers and single walled carbon nanotubes showed high voltage window (2.2 V) with maximum gravimetric capacitance of 111.5 Fg^-1.