Abstract: The solubilization of pyrene in perfluorooctoate micelles with addition of N(C_2H_5)_4Br,N(C_4H_9) (C_2H_5)_3Br and N(C_4H_9)_4Br have been studied by steady fluorescence measurements. The results show that the perfluorooctoate micelles can solubilize pyrene, and the maximal amount of pyrene solubilized is increased considerably on the addition of the alkylammonium bromide; the perfluo-micelles quench the fluorescence of pyrene solubilized into it; the solubilizing sites are all near the stern layer of the micelles, and can be changed by the addition of the alkylammonium with different hydrophobicity due to the stronger interaction between pyrene and the hydrocarbon of the ammonium than that between pyrene and fluorocarbon chain of the surfactant.