An isolable and ambient stable bay-substituted perylene diimide adical anion salt was straightforwardly synthesized by base catalysis reduction of N,N-diethylhexyl-1,7-di(pentafluoro-phenoxyl) perylene diimide (DFPDI) in polar solvents, such as acetone, DMF, DMSO, NMP in yields of 48.7 %. Elemental analysis and H-1 NMR, C-13 NMR and EPR were carried out to confirm the formation of the compounds. Solvent-dependent cyclic voltammetries revealed the only condition for generating DFPDI radical anion in polar solvents-the reduction potential (DFPDI/DFPDI-) is more positive than -0.36 V (vs. Ag/AgCl). Redox studies revealed that DFPDI radical anion was not only ambient stable to moderate oxidants air (O-2) and moisture for prolonged existence but also sensitive to strong oxidants-acid H+ and strong oxidization metal ions with low limit value.