An underlying negative electrode material of beta-Bi2O3 has been designed according to the electrode potential, and synthesized via the combination of a similar hydrothermal method and subsequent annealing treatment. The electrochemical evaluation shows that the metastable phase of beta-Bi2O3 electrode possessing a wide potential window between 1.5 V to 1.5 V in neutral electrolyte manifests satisfying capacity of 871.2C g (1), superior specific energy of 266 Wh kg (1), outstanding rate capability and excellent cycling stability, which confirms this design and provides a feasible method for later design of negative electrode materials. Based on the morphological characteristics and electrochemical measurements, a possible mechanism is proposed that it'll more conducive to electrochemical behavior for particles owning smooth surface. Also, as an electrochemical application, an electrochemical energy storage device has been assembled, where MnO2 and the beta-Bi2O3 acted as the positive and the negative electrodes, respectively, and the specific energy of 32.4 Wh kg (1) is demonstrated at a cell voltage between 0 V to 1.8 V, exhibiting a high energy density and stable power characteristic, which revealed that such a material is promising in electrochemical energy storage applications. (C) 2016 Elsevier Ltd. All rights reserved.