Fluorous biphase system(FBS) formed by organic solvents and perfluorous nonene(PFN) or perfluorous hexane(PFH) and toluene nitration were investigated. The effects of nitration system, reaction time and temperature, perfluorous solvent on yield and ratio of p-nitrotoluene to o-nitrotoluene(R_p-/o-) were studied. PFN or PFH forms binary FBS with ethyl ether, tetrachloromethane, n-heptane and toluene respectively. The critical mutual soluble temperature depends on the contents of FBS. The yield is 93.8% and R_p-/o- is 0.66 in toluene nitration or n_toluene：n_HNO3：n_H2SO4：n_PFH=1：1：0.2：2.0 at 50 ℃ for 4 h. The perfluorous solvents can be recovered by simple phase separation and reused.