Ab initio UMP2, RMP2, DFT/'IJB3LYP, and CBS-QB3 calculations have shown that the adiabatic potential energy surface (PES) of the 1,2,3-trifluorobenzene radical anion is a psendorotation surface formed by nonplanar stationary structures. The low (∼ 2-4 kcal/mol) energy barriers in the path of pseudorotation imply manifestations of spectral exchange in the ESR spectra of this radical anion. The optically detected ESR of radical ion pairs was used to obtain the ESR spectrum of 1,2,3-trifluorobenzene radical anion in liquid squalane solution and to study temperature variations in the spectrum over the range of 243-325 K. The spectrum is a doublet of triplets with hfc constants of a(F(2)) = 29 mT and a(2F(1,3)) = 7.6 mT at T = 243 K. The experimental hfc constants are temperature-dependent. Calculations of the temperature dependence of hfc constants in the framework of the model of classical nuclei motion along the pseudorotation coordinate reproduce well the experimental data.