The valence band (VB) electronic structures of CrSi2 were studied by synchrotron radiation photoemission. Overall features of the VB photoemission spectra measured at room temperature (RT) and 20 K by using synchrotron radiation. (photon energy, h nu = 20-130 eV) were similar. Two characteristic emissions were observed corresponding to the bonding and the nonbonding Cr-d partial density of states (PDOS) in the CrSi2. The onset of the VB photoemission measured at 20 K was located at about 0.32 eV below Fermi level, due to the energy band gap of CrSi2 more than 0.32 eV, (C) 1999 Elsevier Science B.V, All rights reserved.