A novel cationic fluorinated polyacrylate emulsion (CFBDH) was prepared by polymerization of dodecafluoroheptyl methacrylate (DFMA) with butyl acrylate (BA), dimethylaminoethyl methacrylate (DM), and 2‐hydroxypropyl acrylate (HpA) via seeded emulsion polymerization. Chemical structure, particle morphology, glass transition temperature, and thermal property of resultant CFBDH were characterized by FTIR, 1H‐NMR, TEM, DSC, and TGA, respectively. The as‐synthesized product was utilized to treat the clean glass sheet and cotton fabric substrates, then morphology, components, hydrophobicity, and other performances of films on those substrates were investigated by SEM, AFM, XPS, and contact angle meter, etc. Results show that the target product possesses anticipative structure and its latex particles have uniform spherical core‐shell structure with an average diameter of 126 nm. The core‐shell CFBDH latex film thus has two Tg and its thermal property has been improved due to the introduction of fluorine‐containing acrylate monomer. The CFBDH film on cotton fabric surface seems to be smooth compared to the blank by SEM. However, the CFBDH film on silicon‐wafer is inhomogeneous and has many low or high peaks. At 2 nm data scale and in 1 μm2 scanning field, the root mean square roughness of CFBDH film reaches to 0.205 nm. XPS analysis indicates the perfluoroalkyl groups have the tendency to enrich at the film‐air interface. In addition, CFBDH can provide good hydrophobicity for the treated fabric and do not influence whiteness of the treated fabric indeed. However it will make the treated fabric slightly stiff at high doses. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012