To produce the free-standing electrodes, a binder-free direct growth method was employed for electrode fabrication. A NiCo2O4@Ni-MOF (metal–organic framework) composite was synthesized using a one-pot hydrothermal method. Initially, a NiCo2O4 nanowire array was cultivated on Ni foam, serving as a connecting bridge to ensure robust adherence of the Ni-MOF to the substrate. The structures of NiCo2O4 nanowire arrays exhibit the capacity for numerous redox reactions. Hybridizing MOF with transition metal oxide (TMO) nanoarchitectures can significantly alleviate the small specific surface area and aggregation tendency of TMOs. The highest energy storage capacity was obtained when the ratio of nickel to terephthalic acid (TPA) was 4:1. NiCo2O4@Ni-MOF (Ni:TPA=4:1) exhibited a high storage capacitance of 1700F/g. The integration of MOF with TMO nanoarchitectonics as materials for supercapacitor electrodes can enhance porous structure and facilitate diffusion during both charging and discharging processes.