Irradiation of C-60-toluene solution at room temperature affords two ESR bands with g and Delta H-pp values of (2.0013, 0.5 G) and (2.0024, 0.75 G), respectively. In the presence of 6% methanol or 12% benzonitrile, the latter band disappears completely. Below 200 K, only the former band was observed. They were assigned to be C-3(60) and C-60(.+), respectively. In the presence of tetraphenylphosphonium tetraphenylborate, the g value of the C-60(.+) cation radical shifts to 2.0006, and an additional broad band of g = 1.9992 and Delta H-pp = 30 G was observed. Upon cooling, the line width of this new band drops from 30 G at 300 K to 4 G at 77 K. This new band was assigned to be the C-60(.-) anion radical according to its characteristic behavior. At room temperature, photolysis causes the C-60-toluene solution’s color to turn from purple to brown, and then brown precipitates formed. Desorption chemical ionization (DCI) mass analysis of the brown precipitates indicates the formation of C-60. H-u(tolyl)(n)(n = 1-4) adducts. The formation of C-60(.+) and C-60(.-) was rationalized in terms of disproportionation of two C-3(60). The brown precipitates were due to the chemical reaction between the C-60(.+) cation radical and the solvent molecules, which rationalizes the "photodegradation" of fullerene as reported in literature. The important role of the C-60(.+) and C-60(.-) to the peculiar photochemical behavior of fullerene solutions or films, such as nonlinear optical property, photoinduced polymerization in solid film, nonlinear photoconductivity, etc, will be discussed.