X-ray photoelectron spectroscopy and Auger spectroscopy studies of gas-phase hexamethyldisiloxane (HMDSO) are presented. The photodissociation of this molecule is studied using various experimental coincidence techniques. We compare the fragmentation pathways observed after core ionization followed by Auger decay and after valence double photoionization of the molecule. A strongly selective production of the doubly charged tetramethyldisiloxane ion is observed in the low binding-energy regions. Theoretical calculations are carried out to tentatively explain the stability of the produced dication.