Reproducing colors with rich saturation, from illuminating objects, is usually recognized as an essential issue for CCD camera imaging. In this paper, we propose a colorimetric calibration scheme regarding self-luminous images for CCD cameras. And, an efficient algorithm to generate highly saturated color stimuli is devised for investigating the CCD camera performance of image reproduction. In this scheme, a set of color samples containing highly saturated colors is generated, from an advanced CRT, as color stimuli for colorimetric characterization. To demonstrate the effectiveness of this algorithm, a realization of color samples, uniformly distributed in CIE LAB, are presented for illustration.