Fluorination of resist materials is an effective method used to enhance the energy deposition of extreme ultraviolet (EUV) light in the fabrication of next-generation semiconductor devices. The dynamics of radical ions are important to understand when considering the radiation-chemistry of the resist materials using EUV and electron beam lithography. Here, the dynamics of the radical anions and cations of benzenes with one or two 2-hydroxyhexafluoroisopropyl groups (HFABs) were studied using radiolysis techniques. The formation of dimer radical cations was observed only in the monosubstituted benzene solutions of 1,2-dichloroethane. If the compound contained more than two substituents, it was found to hinder the necessary π-π overlapping. Pulse radiolysis of HFABs in tetrahydrofuran showed a characteristic spectral shift of the radical anion within the region of several hundred nanoseconds. From the results of low-temperature spectroscopy and density functional calculations, it is suggested that excess electrons of the 2-hydroxyhexafluoroisopropyl group of the radical anions cause dissociation into neutral radicals.