A detailed investigation to understand the mechanism of the resist action at a fundamental level is essential for future Extreme Ultraviolet Lithography (EUVL) resists. The photodynamics study of a newly developed hybrid nonchemically amplified 2.15%-MAPDSA–MAPDST resist using synchrotron radiation excitation at 103.5 eV (12 nm) is presented. Antimony was incorporated in the resist as a heavy metal absorption center in the form of antimonate (2.15%). The results showed the fast decomposition rate of the radiation sensitive sulfonium triflate. HR-XPS and sulfur L-NEXAFS spectra of the copolymer films revealed that after irradiation the Ar–S⁺–(CH₃)₂ sulfonium group bonded to the phenyl ring resisted the EUV excitation. Those results confirmed the polarity switching mechanism from hydrophilic sulfonium triflates to hydrophobic aromatic sulfides obtained in previous results. The inorganic component SbF₆⁻ included in the resist formulations as an EUV absorption enhancer was particularly illustrative of the photofragmentation process. F 1s and O 1s HR-XPS spectra showed that fluorine remains linked to the antimony, even after 15 min of irradiation. A change of the antimony oxidation state was also observed with an increase in irradiation time. The presence of the heavy metal may control the high energy deposited on the resist which finally led to very well resolved 20 nm isolated line patterns by EUVL. The 10 times improved sensitivity compared with previous poly-MAPDST resists studied in the past showed the potential of this class of hybrid resists for next generation semiconductor industry applications.