Controlling the morphology and size of α-MoO3 is crucial to obtain superior electrochemical properties for electrochemical energy storage and conversion devices. Herein, one, two and three-dimensional α-MoO3 have been controllably synthesized on a large scale with templates via a facile hydrothermal method, and the growth mechanism was investigated and discussed. These three α-MoO3 exhibit excellent pseudo-capacitive energy storage capability and long cycle life. The α-MoO3 nanorod not only has the best pseudocapacitance among as-prepared α-MoO3, but also demonstrates much higher capacitance than those of reported α-MoO3 nanostructures by 2–4 times. Our findings provide an effective solution for the controlled synthesis of different structures of α-MoO3, which can pave the way to further improve the energy storage and energy conversion efficiency of MoO3-based devices. This facile route could be potentially applied to rationally design other high performance oriented oxides.