Electron-ion coincidence technique (PEPICO) and synchrotron radiation have been employed in the study of the ionic fragmentation of epichlorohydrin (C3H5ClO) molecule. Total ion yield and mass spectra have been recorded for the first time for this molecule in the vicinity of the C 1s, O 1s and Cl 1s core excitation edges. We have found evidences of site selective fragmentation upon core excitation, as well as indication of molecular quasi-alignment in the photoexcitation and dissociation at the Cl 1s resonance. © 2006 Elsevier B.V. All rights reserved.