Site-specific fragmentation caused by Si:2p core-level photoionization of F3SiCH2CH2Si(CH3)3 vapor was studied by means of high-resolution energy-selected-electron photoion-photoion triple-coincidence spectroscopy. The ab initio molecular orbital method was used for the theoretical description. F3SiCH2CH2+- Si(CH3)3+ ion pairs were produced by the 2p photoionization of the Si atoms bonded to the three methyl groups, and SiF+-containing ion pairs were produced by the 2p photoionization of the Si atoms bonded to the three F atoms.