Abstract The local structure of solid and molten SrCl 2 was investigated by X-ray absorption fine structure technique. According to the curve fitting analysis with assessment of the anharmonic vibration effect, the nearest Sr 2+ –Cl − distance and the coordination number are 2.99 ± 0.01 A and 6.6 ± 0.2 in molten state. XAFS functions calculated from molecular dynamics simulation results were compared with the experimental XAFS data.