The photoionization of SiCl4 has been investigated in the valence and Si:2p inner-shell region using time-of-flight mass spectrometry and synchrotron radiation in the range 38-133 eV, Ion yields and branching ratios are reported for charged species arising from the dissociative photoionization processes. Various monocations such as Cl+, Cl-2(+), and SiCln+ (n = 0-4) are observed together with doubly charged species such as Si2+, Cl2+, and SiCl2+. The photoion-photoion coincidence (PIPICO) technique has been employed to investigate a variety of dissociation processes via Coulomb explosion and to elucidate the dissociation mechanisms. Ion pairs of Si+ + Cl+ and SiCl+ + Cl+ are observed dominantly in the Si:2p edge. Variation of the ionic fragmentation its a function of photon energy is discussed in conjunction with the relevant electronic states.