Fluorinated polyacrylate latexes are preferably potential materials for use in the textile finishing due to their special surface property and especially economical, low-toxic characteristics compared to fluorinated polyacrylate solutions. A novel cationic fluorine-containing polyacrylate soap-free latex (CFMBD) with core-shell structure was accordingly developed by co-polymerizing dodecafluoroheptyl methacrylate (DFMA), methyl methacrylate (MMA), butyl acrylate (BA), and dimethylaminoethyl methacrylate (DM) using a cationic reactive emulsifier, maleic acid double ester-octadecyl poly(ethyleneoxy)20 ether-ethylene trimethyl ammonium chloride (R303). Then CFMBD was utilized to treat the cotton fabric. Results showed that the as-prepared latex had due structure and its particles had uniform spherical core-shell structure with an average diameter of 125 nm. The core-shell CFMBD latex film thus had two T g and its thermal property was improved due to the introduction of DFMA. CFMBD could form a smooth resin film on the treated fabric/fiber surface under FESEM observation. XPS analysis indicated the fluoroalkyl groups had the tendency to enrich at the film-air interface. Hydrophobicity of the CFMBD treated fabric was slightly superior to that of the fabric treated by general emulsion but their oleophobicity was identical. Contact angles of water and diiodomethane on the CFMBD treated fabric surface could attain 133.5 ° and 105.5 °, respectively. However, washing durability of the treated fabric by CFMBD showed improvement compared to the general emulsion. In addition, CFMBD didn’t influence whiteness of the treated fabric but would make it slightly stiff at high doses.