A hierarchically porous NiO film on nickel foam substrate is prepared by a facile ammonia-evaporation method. The self-assembled film possesses a structure consisting of NiO triangular prisms and randomly porous NiO nanoflakes. The pseudocapacitive behaviors of the porous NiO film are investigated by cyclic voltammograms and galvanostatic charge–discharge tests in 1M KOH. The hierarchically porous NiO film exhibits a high discharge capacitance and excellent rate capability with 232Fg−1, 229Fg−1, 213Fg−1 and 200Fg−1 at 2, 4, 10, and 20Ag−1, respectively. The specific capacitance of 87% is maintained from 2Ag−1 to 20Ag−1. The porous NiO film also shows rather good cycling stability and exhibits a specific capacitance of 348Fg−1 after 4000 cycles.