Density functional theory (DFT) and Time Dependent DFT calculations on triphenyl sulfonium cation (TPS) and the salts of TPS with triflate, nonaflate, perfluoro-1-octanesulfonate and hexafluoro antimonate anions are presented. These systems are widely used as cationic photoinitiators and as electron ejection layer for polymer light-emitting diodes. While some differences exist in the electronic structure of the different salts, their lowest energy intense absorption maxima are calculated at nearly the same energy for all systems. The first excited state of TPS and of the TPS salts is dissociating. Electron addition to the TPS salts lowers their energy by 1.0-1.33 eV.