A lithium-ion hybrid supercapacitor (Li-HSC) comprising a Li-ion battery type anode and an electrochemical double layer capacitance (EDLC) type cathode has attracted much interest because it accomplishes a large energy density without compromising the power density. But instead of using a conventional Li-ion battery type anode we introduce a perovskite based anodes where ions migrate through the perovskite lattice, allowing for a variety of electrochemical applications. It is still unknown how lithium ions interact with the perovskite structure during the charging discharging process. In this work, carbon coated BiFeO₃ (BiFeO₃/C) with a unique mesoporous structure is synthesized through autocombustion using glucose as carbon source and metal-organic framework derived carbon (MOF-C) are prepared, adopted as the anode and the cathode for Li-HSCs. The mesoporous BiFeO₃/C microspheres exhibit higher Coulombic capacity, excellent rate performance and a long cycling life because of storage reactions based on conversion instead of Li⁺ insertion or alloying. The BiFeO₃/C structure shows a reversible specific capacity of 708 mA h g⁻¹ at a current density 10 mAg^-1after 100 discharging-charging cycles with excellent rate performance. The MOF-C achieved the specific capacity of 250.9 F g⁻¹ at a current density of 0.1 A g⁻¹. At a high current density of 2 A g⁻¹, 90% of the initial capacity could be retained after 1000 discharging–charging cycles, suggesting excellent cycle stability. The Li-HSC comprising a BiFeO₃/C anode and a MOF-C cathode boasts a large energy density with a high power density o and 90% of the capacity is retained at a current density of 2 A g⁻¹ after 1000 charging discharging cycles. The high energy and power densities of the Li-HSCs of BiFeO₃/C//MOF-C demonstrate a large potential in energy storage.