We present a series of photoabsorption and partial-ion-yield experiments on thionyl chloride, SOCl2, at both the sulfur and chlorine K edges. The photoabsorption results exhibit better resolution than previously published data, leading to alternate spectral assignments for some of the features, particularly in the Rydberg-series region. Based on measured fragmentation patterns, we suggest the LUMO, of a′ character, is delocalized over the entire molecular skeleton. Unusual behavior of the S2 fragment hints at a relatively localized bond rupture (the S-O bond below the S K edge and the S-Cl bonds below the Cl K edge) following excitation to some of the higher lying intermediate states. © 2012 American Institute of Physics.