The hydrophobically associating cationic fluorinated polyacrylamide (CFPAM), modified with fluorinated acrylate, 2-(perfluorooctyl)ethyl acrylate (FEA), has been newly synthesized, by free radical micellar copolymerization in aqueous solution. The solution properties of these polymers were investigated in details in this study. In addition, the flocculation of CFPAM was also evaluated. The results showed that there were strong hydrophobic associations in the CFPAM aqueous solution. The addition of NaCl resulted in an increase of solution viscosity, which indicated the good salt-resistant performance of CFPAM. The polymers also exhibited excellent property of temperature and shearing tolerance. Furthermore, the polymer showed high surface activity. At the same time, its flocculation properties were evaluated with kaolin suspensions using a standard jar test. All the results demonstrated the superiority of the cationic fluorinated polyacrylamide as a flocculant.