Three novel types of thiophene-containing oxime sulfonates with a big -conjugated system were reported as non-ionic photoacid generators. The irradiation of the newly synthesized photoacid generators using near UV-visible light-emitting diodes (LEDs) (365-475 nm) results in the cleavage of two weak NO bonds in single molecules, which lead to the generation of different sulfonic acids in good quantum and chemical yields. The mechanism for the NO bond cleavage for acid generation was supported by the UV-visible spectra and real-time H-1 NMR spectra. They are developed as high-performance photoinitiators without any additives for the cationic polymerization of epoxide and vinyl ether upon exposure to near-UV and visible LEDs (365-475 nm) at low concentration. In the field of photopolymerization, especially visible light polymerization, it has great potential for application. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 776-782