ArF excimer laser lithography was introduced to fabricate nanometer-scale devices and uses chemically amplified photoresist polymers including photoacid generators (PAGs). Because plasma-etching processes cause serious problems related to the use of ArF photoresists, such as line-edge roughness and low etching selectivity, we have to understand the interaction between plasma and ArF photoresist polymers. Investigating the effects of surface temperature and the irradiation species from plasma, we have found that ion irradiation by itself did not drastically increase the roughness or etching rate of ArF photoresist films unless it was combined with ultraviolet/vacuum ultraviolet (UV/VUV) photon irradiation. The structures of ArF photoresist polymers were largely unchanged by ion irradiation alone but were destroyed by combinations of ion and UV/VUV-photon irradiation. Our results suggested that PAG-mediated deprotection induced by UV/VUV-photon irradiation was amplified at surface temperatures above 100 °C. The etching rate and surface roughness of plasma-etched ArF photoresists are affected by the irradiation species and surface temperature during plasma etching. UV/VUV-photon irradiation plays a particularly important role in the interaction between plasma and ArF photoresist polymers.