X-ray absorption spectroscopy study of crystalline ReO3 was performed at the Re L3-edge in the temperature interval from 77 to 670 K. The analysis of both XANES and EXAFS regions shows that in ReO3, a progressive localization of the 5d states following the temperature increase is accompanied at T > 350 K by a distortion of the ReO6 octahedra. The distortion increases continuously up to the ReO3 decomposition temperature Td≈ 673 K and leads to the lowering of the rheniurn site symmetry from Oh(T≤350K) →D4h(T≈513K)→C4v(T≈668K). The observed distortion is explained by (i) the strong electron-phonon coupling of the 5d electron with the M3 and M'z3 phonons and (ii) the Jahn-Teller-like effect caused by the rhenium 5d1 electron which becomes localized at high temperature