A metal–organic framework (MOF) is a highly porous material with abundant redox capacitive sites for intercalation/de-intercalation of charges and, hence, is considered promising for electrode materials in supercapacitors. In addition, dopants can introduce defects and alter the electronic structure of the MOF, which can affect its surface reactivity and electrochemical properties. Herein, we report a copper-doped iron-based MOF (Cu@Fe-MOF/NF) thin film obtained via a simple drop-cast route on a 3D-nickel foam (NF) substrate for the supercapacitor application. The as-deposited Cu@Fe-MOF/NF electrodes exhibit a unique micro-sized bipyramidal structure composited with nanoparticles, revealing a high specific capacitance of 420.54 F g−1at 3 A g−1which is twice compared to the nano-cuboidal Fe-MOF/NF (210 F g−1). Furthermore, the asymmetric solid-state (ASSSC) supercapacitor device, derived from the assembly of Cu@Fe-MOF/NFǁrGO/NF electrodes, demonstrates superior performance in terms of energy density (44.20 Wh.kg−1) and electrochemical charge–discharge cycling durability with 88% capacitance retention after 5000 cycles. This work, thus, demonstrates a high potentiality of the Cu@Fe-MOF/NF film electrodes in electrochemical energy-storing devices.