The hierarchically porous materials have led to a significant improvement in the applications of electrochemical energy conversion and storage, owing to their outstanding properties, such as high surface area, admirable ease of access to active sites, enhanced mass transport and diffusion. Hence, a significant attention has been diverted towards the synthesis of hierarchically porous nanostructured materials using various methods. Here, we report a novel, simple, scalable and robust solvent deficient approach for the synthesis of hierarchical mesoporous network of amorphous alpha - Ni(OH)(2), using Ni (NO3)(2)center dot 6H(2)O in the presence of ammonium bicarbonate as well as sodium bicarbonate, separately. The X-ray diffraction, Raman and FTIR studies confirms the formation of amorphous alpha - Ni(OH)(2). The obtained mesoporous network shows the hierarchical pore size and pore volume distribution depending on the size of different spectator ions evolved during the process. The hierarchical mesoporous network is perceived from the TEM and BET analysis. The SAED pattern endorses for the amorphous nature of the samples. Furthermore, the electrochemical properties exhibit the maximum specific capacitance 2338 Fg(-1) and 231 Fg(-1) for alpha - Ni(OH)(2) obtained from ammonium bicarbonate and sodium bicarbonate, respectively. Through various measurements, it has been corroborated that, the different bicarbonate used during the synthesis in solvent deficient environment strongly affects the pore size distribution and hence the electrochemical performance. In addition, the high performing electrode material has been utilized as an anode material in the asymmetric supercapacitor shows good capacitive behavior with a cycling stability of 91.08% after 5000 CV cycles. (C) 2017 Elsevier Ltd. All rights reserved.