The effective Debye temperatures (θDE) of the surface region of UO2 single crystals, prepared by the hydrothermal synthesis technique, were obtained from temperature-dependent x-ray photoemission in the temperature range of 300 K–623 K. A lattice stiffening transition, characterized by different regions of different effective Debye temperature, 500 ± 59 K below 475 K and 165 ± 21 K above 475 K is identified. A comparison of the temperature dependence of the effective UO2 Debye temperature, with the changes in the lattice expansion coefficient for UO2, support strong lattice-phonon interaction arising from the Jahn–Teller distortion