Abstract: The CCD’s optics-electron characteristic is an important parameter when it is applied to measuring the energy distribution of laser’s far-field and near-field. A new method of calibrating the CCD’s optics-electron characteristic is introduced in this paper. The method uses the zeroth order energy-distribution caused by the pinhole diffraction as the CCD’s fiducial input energy. According to the CCD’s output data sampling the pinhole diffraction, the optics-electron characteristic curve is calculated through the least-square algorithm. The data process procedure, the validation experimental result and the analysis of its residual error are presented.