Synchrotron-radiation photoemission and inverse photoemission spectroscopies are powerful techniques to investigate occupied and unoccupied electronic states of solids. In this paper, we demonstrate that in situ measurements of ultraviolet photoemission and inverse photoemission spectra are successfully applied to studies of semiconductors. Our experimental results for Cd1-xMnxTe, zincblende (ZB-) and hexagonal NiAs-type (H-) MnTe, trigonal (t-) and glassy (g-) Se, and g-GexSe1-x and g-AsxSe1-x are presented to discuss the Mn 3d spin-exchange splitting energy and degree of hybridization between Mn 3d and sp-band states in Cd1-xMnxTe, ZB- and H-MnTe, dominant source of the distinct difference of electronic structures between t- and g-Se, and percolation phenomenon in non-crystalline covalent networks in g-GexSe1-x and g-AsxSe1-x, respectively.