Mn-doped TiO2 micro/nanostructure porous film was prepared by anodizing a Ti-Mn alloy. The film annealed at 300 °C yields the highest areal capacitance of 1451.3 mF/cm(2) at a current density of 3 mA/cm(2) when used as a high-performance supercapacitor electrode. Areal capacitance retention is 63.7% when the current density increases from 3 to 20 mA/cm(2), and the capacitance retention is 88.1% after 5,000 cycles. The superior areal capacitance of the porous film is derived from the brush-like metal substrate, which could greatly increase the contact area, improve the charge transport ability at the oxide layer/metal substrate interface, and thereby significantly enhance the electrochemical activities toward high performance energy storage. Additionally, the effects of manganese content and specific surface area of the porous film on the supercapacitive performance were also investigated in this work.