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A new interpretation of the acid generation process in novolak resin systems is reported. To investigate the acid generation process in chemically amplified resist, a novolak resin system with an acid generator (PAG) was employed. In order to analyze the acid generation process, the visible absorption characteristics from a conventional spectrophotometer, and nanosecond and millisecond pulse radiolysis systems, were analyzed. For m‐cresol novolak with triphenylsulfonium triflate, it was hypothesized that acid would be generated during exposure; however, it is asserted that a protonated intermediate was generated during exposure and that acid was generated during exposure, and more acid was formed during PEB. The yield of the acid during PEB, rather than that of the protonated intermediate during exposure, was strongly influenced by the presence of triphenylamine. A comparison of the experimental result for m‐cresol novolak which contains PAG with that for p‐cresol novolak which also contains PAG indicates that the time range of acid generation may be dependent on the base resin system.