In past decades,the performance of supercapacitors has been greatly improved by rationalizing the elec-trode materials at the nanoscale.However,there is still a lack of understanding on how the charges are efficiently stored in the electrodes or transported across the electrolyte/electrode interface.As it is very challenging to investigate the ion-involved physical and chemical processes with single experiment or computation,combining advanced analytic techniques with electrochemical measurements,i.e.,develop-ing in-situ characterizations,have shown considerable prospect for the better understanding of behaviors of ions in electrodes for supercapacitors.Herein,we briefly review several typical in-situ techniques and the mechanisms these techniques reveal in charge storage mechanisms specifically in supercapacitors.Possible strategies for designing better electrode materials are also discussed.