Heteropoly blue-intercalated layered double hydroxide (HB-LDH) was obtained by aqueous ion exchange of a Zn–Al LDH precursor in nitrate form with the reduced polyoxometalate anions [PW 10 Mo 2 O 40 ] 5− . The physicochemical properties of the product were characterized by the methods of powder X-ray diffraction, infrared spectroscopy, and cyclic voltammetry. The HB-LDH has been used for the removal of cationic dye methylene blue (MB) from aqueous solutions via adsorption. The intercalation of large cluster anion [PW 10 Mo 2 O 40 ] 5− into LDH could induce the adsorption to cationic dye of MB, obviously. The HB-LDH shows much higher cationic dye adsorption capacity than pure LDH and the maximum adsorption capacity Q max of MB onto ZnAl–PW 10 Mo 2 is 30.87mg/g.