Electroactive materials with hollow nanostructures received great attractiveness due to large surface area, low density and superior structure permeablity. The paper reported a new template synthesis of nickel/cobalt layered double hydroxides (Ni/Co-LDH) without any adscititious alkali source, oxidant and step for removal of the template. Nickel nitrate, cobalt nitrate and SiO2 nanosphere were dispersed in an ethanol solution. Then, the mixed soution was heated at 160°C for 6h to obtain Ni/Co-LDH product. During the process, ethanol and nitrate underwent a redox reaction releasing hydroxide ions, which will react with nickel and cobalt ions to form ultrathin Ni/Co-LDH nanoflakes. Meanwhile, SiO2 template was gently dissolved by hydroxide ions. Interestingly, perfect match between generation rate of Ni/Co-LDH nanoflakes and removal rate of the template creates an elaborate three-dimensional structure with well-defined hollow interior and hydrangea-like exterior. The unique structure will greatly improve electron and mass transfer during the faradic redox reaction. The Ni/Co-LDH electrode exhibits excellent electrochemical performance for supercapacitors. Its specific capacitance is up to 2158.7Fg−1 at the current density of 1Ag−1 and 1965.6Fg−1 at the current density of 5Ag−1. The capacitance can keep at least 97.5% of initial value after 1500 cycles. The study also provides prominent approach for the fabrication of hollow nanomaterials with three-dimensional structure for supercapacitors, Li-ion batteries, catalyst and sensors.