Metal−organic frameworks (MOFs) are of great interest for energy applications due to their high porosity, high charge storage capacity, and large number of active redox sites. It is important to enhance the performance of metal−organic frameworks through modification in order to increase their potential applications. Unique Fe nanoparticle (NP) in the Materials of Institute Lavoisier (MIL) series embedded in the carbon nanotube (CNT), FeNP@MIL-101(Fe)/CNT-based, nanocomposites have been synthesized using suitable hierarchical micromesoporous structures. These were fabricated by simple and straightforward solvothermal methods, and their electrochemical charge storage performance was investigated. The energy storage application using the FeNP@MIL −101(Fe)/CNT composite as a supercapacitor electrode was implemented for the first time. Various techniques were used to characterize this composite. It has excellent electrochemical properties when used as electrode material in 1 M KOH solution, including a high capacitance of up to 1305 F g −1 at 1 A g −1 and a long cycling stability of 95.7% capacitance retention after 10,000 cycles. Moreover, symmetric two-electrode electrochemical experiments showed that the composite achieved an energy density of 98.65 Wh kg −1 and a power density of 9000 W kg −1 , The combination of microporous and mesoporous structures, increased surface area, and higher electrical conductivity are the main reasons for the high performance. The integration of FeNP@ MIL-101(Fe) with the CNT creates new ion diffusion pathways, improves the hierarchical pore properties, and exposes the FeNP@ MIL-101(Fe) cluster to more redox active sites, which improves the charge storage performance.