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 it pi-pi overlapping. Pulse radiolysis of HFABs in tetrahydrofuran showed 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.