Multi-walled carbon nanotubes (MWCNTs) were partially unzipped longitudinally by a chemical method. Unzipped multi-walled carbon nanotubes (UZ-MWCNTs) were characterized by transmission electron microscopic analysis, X-ray diffraction and Raman spectroscopic analyses. UZ-MWCNTs were utilized for electrode preparation and the electrodes were used in the fabrication of a supercapacitor. At room temperature, the UZ-MWCNTs based supercapacitor showed a specific capacitance of ∼41 F g⁻¹, while pristine MWCNTs based supercapacitor exhibited 22 F g⁻¹ at the scan rate of 25 mV s⁻¹. The increase in specific capacitance was attributed to an increase in effective specific surface area of UZ-MWCNTs due to partial unzipping. UZ-MWCNTs based supercapacitor exhibited an increase in specific capacitance with increase in temperature. It showed a specific capacitance of ∼74 F g⁻¹ at 100 °C at the scan rate of 25 mV s⁻¹, while the pristine MWCNTs based supercapacitor did not show any appreciable change in specific capacitance as a function of temperature. UZ-MWCNTs exhibited three-fold increase in specific capacitance as compared to pristine MWCNTs at 100 °C. Impedance spectroscopic analysis of the supercapacitors revealed that the UZ-MWCNTs based supercapacitor exhibited higher internal resistance and lower leakage resistance than pristine MWCNTs based supercapacitor. Continuous ‘charge–discharge’ cycling behaviour indicated that the UZ-MWCNTs based supercapacitor exhibited less stability during initial cycles even though it depicted higher specific capacitance as compared to the pristine MWCNTs based supercapacitor.