Cationic fluorinated polyacrylate emulsifier-free emulsion was synthesized by ab initio RAFT emulsifier-free emulsion polymerization using fluorine-containing amphiphilic block copolymer poly (2-(dimethylamino) ethyl methacrylate)-b-poly (hexafluorobutyl acrylate) (PDMAEMA-b-PHFBA) macro-RAFT agent as a stabilizer, and (2-(acryloyloxy)ethyl)trimethylammonium chloride (DMC) as a cationic monomer. The critical micelle concentration (CMC) of PDMAEMA-b-PHFBA is much smaller than the CMC of SDS, suggesting the excellent micelle-forming ability of PDMAEMA-b-PHFBA in water. The influence of the amount of DMC on emulsion polymerization and finished fabric properties was investigated. The latex particle size and its distribution decreased as the amount of DMC increased from 0 wt% to 2.25 wt%, and then increased afterwards. The cationic fluorinated polyacrylate showed much higher thermal stability than polyacrylate. The water contact angle of the finished fabric decreased with the increase of the amount of DMC. The cationic fluorinated polyacrylate emulsifier-free emulsion was deposited on the surface of fabric characterized by SEM-EDX, and the finished fabrics showed good water repellency. In addition, the finished fabric with fluorinated polyacrylate emulsifier-free emulsion had good antibacterial property against E. coli and S. aureus.