© 2015 American Chemical Society. Hf-based hybrid photoresist materials with three different organic ligands were prepared by a sol-gel-based method, and their patterning mechanism was investigated in detail. All hybrid nanoparticle resists are patternable using UV exposure. Their particle sizes show a dramatic increase from the initial 3-4 nm to submicron size after exposure, with no apparent inorganic content or thermal property change detected. XPS results showed that the mass percentage of the carboxylic group in the structure of nanoparticles decreased with increasing exposure duration. The particle coarsening sensitivities of those hybrid nanoparticles are consistent with their EUV performance. The current work provides an understanding for the development mechanism and future guidance for the design and processing of high performance resist materials for large-scale microelectronics device fabrication.