The recent fast development of supercapacitors, also known scientifically as electrochemical capacitors, has benefited significantly from synthesis, characterisations and electrochemistry of nanoma-terials. Herein, the principle of supercapacitors is explained in terms of performance characteristics and charge storage mechanisms, i.e. double layer (or interfacial) capacitance and pseudo-capacitance. The semiconductor band model is applied to qualitatively account for the pseudo-capacitance in association with rectangular cyclic voltammograms (CVs) and linear galvanostatic charging and discharging plots (GCDs), aiming to differentiate supercapacitors from rechargeable batteries. The invalidity of using peak shaped CVs and non-linear GCDs for capacitance measurement is highlighted. A selective review is given to the nano-hybrid materials between carbon nanotubes and redox active materials such as electronically conducting polymers and transition metal oxides. A new concept,“interfacial conjugation”, is introduced to reflect the capacitance enhancement resulting from π-π stacking interactions at the interface between two materials with highly conjugated chemical bonds. The prospects of carbon nanotubes and graphenes for supercapacitor applications are briefly compared and discussed. Hopefully, this article can help readers to understand supercapacitors and nano-hybrid materials so that further developments in materials design and synthesis, and device engineering can be more efficient and objective.