Surfmer [3-(acryloylamino)propyl]dodecyldimethyl ammonium bromide (APDDAB) was synthesized and characterized. On the basis of the reverse emulsion polymerization technique, poly[acrylamide-co-3-(acryloylamino)propyldodecyldimethylammonium bromide] [P(AM-co-APDDAB)] copolymer microgels were obtained with the copolymerization of acrylamide and APDDAB. The P(AM-co-APDDAB)/polyoxotungstates composite microspheres were prepared with the ion-exchange reaction of the P(AM-co-APDDAB) microgels with phosphotungstic acid (H3PW12O40). The morphologies and components of the composite microspheres were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The results indicate that the P(AM-co-APDDAB)/PW12O40 composite microspheres all had a core-shell structure. For the composite microspheres, the hydrogel P(AM-co-APDDAB) was dominantly located in the core, and the complexes of PW12O403- with APDDAB were mainly located in the surface; these features made the composite microspheres amphiphilic and provided for potential catalysis in a two-phase reaction. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: 509-516, 2011