The application of porous and conductive composite materials in energy storage devices has received great attention in the recent years. Porous materials, such as metal-organic frameworks (MOFs), possess features like large specific surface area, mesoporous structures, and multiple reaction sites that make them attractive for energy storage devices. Further, the integration of MOFs with suitable conducting agents is a promising strategy to introduce additional conductive pathways in them, which facilitates fast charge transfer. In the present work, we report synthesis and supercapacitor application of a ZIF-67/PEDOT heterostructure composite. The prepared ZIF-67/PEDOT composite, when analyzed for electrochemical performance in three-electrode systems, has delivered a specific capacitance of 106.8 F/g at a current density of 1 A/g. This value is significantly better than that attaintable with only pristine ZIF-67 electrode (34.75 F/g at 1 A/g). Extending the study, two ZIF-67/PEDOT electrodes have been used to assemble an all-solid-state symmetrical supercapacitor, which delivers excellent values of energy density (∼11 Wh/kg) and power density (200 W/kg). Hence, this work paves the way for the potential application of ZIF-67/PEDOT composite in the development of next-generation supercapacitors.