Thermochromic phase transition was studied in CuMoO4 using the Cu and Mo K-edge x-ray absorption spectroscopy in the temperature range of 10-300 K. The hysteretic behavior has been evidenced from the temperature dependence of the pre-edge shoulder intensity at the Mo K-edge, indicating that the transition from brownish-red gamma-CuMoO4 to green alpha-CuMoO4 occurs in the temperature range of 230-280K upon heating, whereas the alpha-to-c transition occurs between 200 and 120K upon cooling. Such behavior of the pre-edge shoulder at the Mo K-edge correlates with the change of molybdenum coordination between distorted tetrahedral in alpha-CuMoO4 and distorted octahedral in c-CuMoO4. This result has been supported by ab initio full-multiple-scattering x-ray absorption near edge structure (XANES) calculations. Published by AIP Publishing.