In situ measurements of ultraviolet photoemission and inverse photoemission spectra are successfully applied to studies of the electronic structure of semiconductors. Our experimental results for diluted magnetic semiconductor Cd1−xMnxTe, zincblende MnTe and hexagonal NiAs-type MnTe are presented to discuss the Mn 3d spin-exchange splitting energy and degree of p–d hybridization. An outline of Hiroshima Synchrotron Radiation Center, which has incorporated activity on photoemission and inverse photoemission spectroscopies, is presented, with its brief history, role, light sources and beamlines.