This paper demonstrates how secondary electron energy spectroscopy (SEES) performed inside a scanning electron microscope (SEM) can be used to map sample atomic number and acquire bulk valence band density of states (DOS) information at low primary beam voltages. The technique uses an electron energy analyser attachment to detect small changes in the shape of the scattered secondary electron (SE) spectrum and extract out fine structure features from it. Close agreement between experimental and theoretical bulk valance band DOS distributions was obtained for six different test samples, where the normalised root mean square deviation ranged from 2.7 to 6.7%. High accuracy levels of this kind do not appear to have been reported before. The results presented in this paper point towards SEES becoming a quantitative material analysis companion tool for low voltage scanning electron microscopy (LVSEM) and providing new applications for Scanning Auger Microscopy (SAM) instruments.