A series of Ni-MOF materials were synthesized via a simple hydrothermal method and can be employed as electrodes for supercapacitors (SCs). Different temperatures were selected to unveil the effect of temperature on the formation, structure, and electrochemical performance of Ni-MOF-x (x = 60, 80, 100, and 120). Ni-MOF-80 possessed a larger specific surface area with a cross-network structure formed on its surface. The synthesized Ni-MOF electrode delivered a specific capacity of 30.89 mA h g−1 when the current density reached 1 A g−1 in a three-electrode system. The as-fabricated Ni-MOF materials could be further designed and are expected to deliver satisfactory performance in practice.