CoFe Prussian blue analogue Rb1.8Co4[Fe(CN)(6)](3.3). 13H(2)O was synthesized, which presents an important photomagnetic effect. The electronic structure and the local structure of the ground and of the excited states have been investigated. X-ray absorption spectroscopy measurements at the Co and Fe L-2.3 edges and cobalt K-edge (XANES and EXAFS) evidence the local electronic transfer and the spin change of the cobalt ions induced by irradiation. We observed a 0.19 Angstrom increase of the Co-N bond length, associated with the transformation of Co-III low spin to Co-II high spin. The Co-II/Co-III ratio has been evaluated as a function of the irradiation time and revealed as an important parameter to understanding the bulk magnetic properties. The combined role of the diamagnetic Fe-II-Co-III pairs and hexacyanoferrate(III) vacancies is locally evidenced. This work is a new step in the understanding of the photoinduced electron transfer.