Photoinduced electron transfer reactions of highly conjugated thiophene derivatives, 4,7-di(2,3-dihydrothieno[3,4-b] [1,4]dioxin-5-yl)benzo[1,2,5]thiadiazole (DTDT) and 5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2,3-di(thiophen-2-yl)quinoxaline (DTDQ), with diphenyl-iodonium hexafluorophosphate (Ph2I+PF6-) and triphenylsulfonium hexafluorophosphate (Ph3S+PF6-) were investigated by laser flash photolysis, fluorescence and phosphorescence spectroscopy, and polymerization studies. High fluorescence quantum yields, long fluorescence lifetimes (similar to 10 ns in aprotic solvents), and absence of detectable phosphorescence at 77 K for both compounds indicate inefficient intersystem crossing into the triplet state and dominant role of singlet excited state. Photolysis of DTDT or DTDQ in the presence of iodonium salt with visible light results in the formation of radical cations of DTDT and DTDQ as detected by laser flash photolysis. Sulfonium salts do not undergo such electron transfer reactions due to the unfavorable redox potentials. The importance of the described photoinduced electron transfer process with respect to the initiation of cationic polymerization and formation of conjugated polymers was demonstrated.