With the development of HVDC Light project since 1990’s, it is necessary to construct the large scale electric power grid with reliable DC insulation system, connecting wind farms to power grid, underground power links, connecting asynchronous grids, etc. Therefore, it is important to propose advanced detection technique under DC high electrical stress, evaluate the space charge characteristics and explore novel insulating materials [1]. This article describes the short developing history of the electric charge accumulation measurement techniques in insulating materials using acoustic and optical methods [2], and the analytical methods using quantum chemical calculation. Some data was also included for further understanding.