The CeB6(001) single crystal used as a cathode in a low-emittance electron gun and operated at the free-electron laser facility SACLA was investigated using cathode lens electron microscopy combined with X-ray spectroscopy at SPring-8 synchrotron radiation facility. Multilateral analysis using thermionic emission electron microscopy, low-energy electron microscopy, ultraviolet and X-ray photoemission electron microscopy and hard X-ray photoemission spectroscopy revealed that the thermionic electrons are emitted strongly and evenly from the CeB6 surface after pre-activation treatment (annealing at 1500°C for >1 h) and that the thermionic emission intensity as well as elemental composition vary between the central area and the edge of the old CeB6 surface.