Although kaolinite-ammonium acetate complexes are of interest in the area of kaolinite nanocomposites, the structures of these complexes have remained largely elusive. Experimental and molecular simulation analysis is used to investigate their structures, revealing that two types of water-containing kaolinite-ammonium acetate complex exist. A cost-efficient one-step homogenization method was used to synthesize these complexes. The effect of the aging time and the amount of reagents on the intercalation were characterized experimentally by X-ray diffraction, thermogravimetry, Fourier transform infrared spectroscopy and scanning electron microscopy. The optimal degree of intercalation was obtained by using two orders of magnitude lower amount of reagents than in the case of the solution method. It was found that the so far less investigated 1.7-nm complex has higher water content than the 1.4-nm one. For both complexes, our molecular simulations predict the double-layered structure of the acetate ions, which is usually assumed in the case of the kaolinite-acetate complexes. For the 1.7-nm complex, however, a quasi-triple-layered structure of water molecules instead of the double-layered one was calculated. (C) 2014 Elsevier Inc. All rights reserved.