The P(AM-co-MAA)/AEM composite microspheres with lichi-like structure were synthesized by the hydrolysis and condensation of 3-(trimethoxysilyI)-propyldimethyloctadecyl-ammonium chloride (AEM) located within porous poly(acrylamide-co-methylacrylic acid) (P(AM-co-MAA)) microgels in an ammonia water atmosphere. The morphology and composition of the composite microspheres were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectrometer (FI-IR), and X-ray photoelectron spectroscopy (XPS), respectively. The results indicated that the composite microspheres with lichi-like surface structure could be obtained by controlling the loaded amount of AEM, the hydrolysis-condensation time of AEM, and the cross-linking degree of the porous P(AM-co-MAA) microgels. On the basis of the results, the mechanism on the formation of the microspheres with lichi-like surface structure was proposed. The multiple factors play a role in the formation of the specific surface morphology. The pores of the porous microgels make AEM behavior localized; the migration of AEM along with solvent evaporation leads to the structural change; the hydrolysiscondensation of AEM brings the temporarily structural solidification; the surface tension of hydrophobic AEM in hydrophilit atmosphere induces AEM liquid membrane constriction. Although the mechanism is complicated, the method is very simple. Based on the analogous principle, other composite materials with lichi-like structure could be constructed by altering precursor and porous template. (C) 2013 Elsevier Inc. All rights reserved.