A photoinduced spin transition state of [Fe-II(2-picorylamine)(3)]Cl-2 . C2H5OH was investigated by Fe K-edge X-ray-absorption fine structure (XAFS) spectroscopy. The X-ray-absorption near-edge structure (XANES) of the photoirradiated sample at 30 K is well reproduced as a superposition of those obtained at 298 and 30 K, corresponding to high-and low-spin phases, respectively. An analysis of the extended X-ray-absorption fine structure (EXAFS) shows that the Fe-N coordination in the photoinduced state is identical with that in the high-spin phase at room temperature, as confirmed by the bond distance and the Debye-Waller factor. (C) 2003 Published by Elsevier Science B.V.