The explosive RDX with high yield (129.4%) was prepared by the perfluorooctanesulfonic acid (C₈F₁₇SO₃H,PfOS)catalyzed nitrolysis of hexamethylenetetramine using perfluorodecalin (C₁₀F₁₈, cis and transmixture) as fluorous solvent. The process produced smaller waste acid and nitrate than that in traditional process. Effects of amount of nitric acid, catalyst, and ammonium nitrate, reaction temperature, reaction time,and the ratio of fluorous phase to water phase on nitrolysis were investigated. Results show that the fluorous system containing 10% PfOS and 0.5 equiv. of ammonium nitrate with 10 equiv. of nitric acid can give the RDX with yield of 129.4% (calculated on the basis of one mole of hexamethylenetetramine producing one mole of RDX ) at 20 ℃ after 6 h. The fluorous phase containing catalyst can be easily and efficiently recovered and reused by simple phase separation.