Metal-Organic Frameworks (MOFs) attract increasing attention in the field of energy storage, however, poor conductivity in most MOFs largely hinders their electrical properties. In this work, an effective strategy is developed to make the polyaniline (PANI) molecular chains grow in the pores of UiO-66 as one of the MOFs (labeled as PANI/UiO-66) to form a fixed interpenetrating network structure by using the highly stable porous MOFs, through a variety of synergistic effects to enhance the conductivity and electrochemical properties. Moreover, the design and analysis about PANI/UiO-66 is reported for the first time to our knowledge. In addition, PANI/UiO-66 exhibits an extraordinary capacitance of 1015 F g(-1) at 1 A g(-1) by electrochemical test. At the same time, the symmetric flexible solid-state supercapacitors is also assembled and tested. The resultant supercapacitor shows a favorable specific capacitance of 647 F g(-1) at 1 A g(-1) and a high cycling stability (91% capacitance retention after 5000 cycles). The bending test indicates that the obtained supercapacitor is flexible and its performance is only decreased 10% after 800 bending cycles with a bending angle of 180. This flexible solid-state supercapacitor shows great potential in energy storage device.