A novel spectroscopy, low energy electron excited soft X-ray spectroscopy (LEEXS) has been demonstrated in surface analysis of Si(100) crystal surfaces. The adoption of glancing angle as the incident angle as well as take-off angle makes it possible to highly detect the X-ray signal from surface top layers. In addition to the surface sensitivity, the use of the low-energy primary electron (600 eV to 2.6 keV) enables a (nondestructive) detection of light elements on the surface with its high sensitivity that has ever been impossible for similar X-ray spectroscopy with high-energy primary electrons. [DOI: 10.1380/ejssnt.2006.443]