Metal-Organic Frameworks (MOFs) have attracted increasing attention in the field of energy storage owing to their high porosity, high specific surface area, high charge storage. However, the poor conductivity in most MOFs largely hinders their electrical properties. In this work, we developed an effective strategy to grow the conductive polyaniline (PANI) inside the pores of MIL-101 (labeled as PANI/MIL-101) to form a fixed interpenetrating network structure. The electron-rich imine group in PANI is chelated with the coordinatively unsaturated metal sites (CUS) in MIL-101 to form a relatively strong bonded complex and through other synergistic effects to enhance the conductivity and electrochemical properties. The resultant PANI/MIL-101 exhibited a superior high capacitance of 1197 F g(-1) (i.e., 957.6C g(-1)) at 1 A g(-1) in constant current charge and discharge test. The assembled flexible solid-state supercapacitor showed a favorable specific capacitance, power density and good cycling stability (a 81% capacitance retention rate over 10,000 cycles). It also demonstrates a good flexibility, as evidenced by a small capacitance loss of 10% after being subject to 1000 bending cycles at 180 degrees. The PANI/MIL-101 nano-composite showed great potential in energy storage device. Crown Copyright (c) 2018 Published by Elsevier Ltd. All rights reserved.