A novel thioxanthone-anthracene (TX-A) photoinitiator possessing an octyl group, TX-A-Oct, as amphipathic photoinitiator was synthesized by click chemistry. Its ability to initiate photopolymerization of various monomers, namely methyl methacrylate (MMA), acryl amide (Am), butyl acrylate (BA), styrene (St), and a multifunctional monomer trimethylolpropane triacrylate (TMPTA), was examined in both the presence and absence of air. TX-A-Oct was found to be effective in initiating polymerization also in the absence of a co-initiator. UV, FTIR, and fluorescence spectroscopic analysis and polymerization studies revealed that depending on the conditions photoinitiations occur through both anthracene and thioxanthone chromophoric groups by hydrogen abstraction and endoperoxide formation processes, respectively.