High-performance electrode materials are long-cherished for electrochemical energy storage, especially the application in supercapacitors. In this work, an efficient and green hydrothermal process followed by calcination is applied for the fast synthesis of hollow amorphous nickel phosphate microspheres. Instead of traditional inorganic phosphorus, adenosine 5′-triphosphate disodium salt (ATP) as organic phosphorus source is employed which is conductive to build hollow microsphere structure as well as pore channels. The formation mechanism of target product is studied thoroughly by exploring the influence of the reaction temperature and time on the morphology and crystallinity. Benefiting from the construction of hollow amorphous microsphere, our nickel phosphate material achieves a remarkable electrochemical performance with the specific capacitance of 1034 F g−1 at the current density of 0.5 A g−1, and the energy density is 26.75 W h kg−1 at a power density of 750.00 W kg−1, which forecasts to be an ideal electrode material in the aspect of energy storage devices.