Complementary information on the valence and conduction states of solids can be obtained by using both soft X-ray (SXS) and X-ray photoelectron (XPS) spectroscopies. From X-ray emission (and absorption) spectra, it is possible to probe local and symmetry-selected valence (and conduction) band states by studying electronic transitions involving a core level and the outer occupied (or unoccupied) electronic states. The results can thus be compared to the XPS valence band spectra which provide the total VB distribution modulated by photoionisation cross-sections. Moreover, the information is quite complementary to that deduced from the optical spectra. The possibilities of these methods are discussed and results obtained for amorphous semiconductors are presented.