The radical anion of pyrazino[2,3-f][1,10] phenanthroline-2,3-dicarbonitrile (PPDN) in blends with imidazolium based room temperature ionic liquids (RTIL): EMIM-DCA, BMIM-BFCH₄, EMIM-Ac has been detected by X-band continues wave (CW) EPR under steady state Xe-lamp illumination in the temperature interval from 190-340 K. The radical anion of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) was registered by X- and K-band CW EPR at room temperature under the visible light CW diode laser operated at 532 nm, and Xe-lamp as well. The experimental hyperfine coupling data of both anion radicals were confirmed by DFT calculation. The formation of PPDN^•-, NTCDA^•- and fullerene derivative (FD) radical anions is attributed to the photoelectron transfer from an IL anion to PPDN, NTCDA and FD electron acceptors. Here, the electron transfer leads to an irreversibility of these reactions due to photo-induced decomposition of the IL anions in the presence of an effective electron acceptor and is supported in the above RTILs solutions by means of EPR. For the indirect confirmation of the EMIM-DCA, EMIM-AC, BMIM-BF₄ anion degradation in solutions with PPDN and NTCDA up to the transient radical state, similar data of acetate anion [OCOCH₃]^- decomposition, under CW Xe-Lamp photolysis resulting in CHCH₃^• formation and its stabilization at 77K in EMIM-Ac suspension with some FD dissolved in DCB are introduced as well. However, the main goal of this study is dedicated to the features of rotational and translational diffusion kinetics of PPDN and NTCDA radical anions in IL solutions as well to the evaluation of their application as a spin probes in ILs study in liquid phase.