The heteropoly acid H6P2W18O62 was introduced into the MIL-101(Fe) by solvothermal synthesis to prepare a new adsorbent H6P2W18O62/MIL-101(Fe), and its adsorption performance for methylene blue (MB) was tested. The adsorption properties of the materials under different conditions such as the loading of H6P2W18O62, the mass concentration of methylene blue solution, the pH value of the solution and the temperature were investigated. The materials were characterized by XRD, SEM, FTIR and N2 adsorption-desorption. The experimental results show that the adsorption capacity increased with the increase of the mass concentration of MB before the adsorption equilibrium, when the loading amount of H6P2W18O62 is 35% of the mass fraction of the composite, the adsorption effect of the adsorbent H6P2W18O62/MIL-101(Fe) on methylene blue solution was the best in solution pH=4. The maximum adsorption capacity of MB by H6P2W18O62/MIL-101(Fe) can reach 148.1 mg/g at 303k. By kinetic and thermodynamic analysis, the adsorption process conforms to the pseudo-second-order kinetics and Langmuir isothermal adsorption model. The adsorption is also an endothermic and spontaneous process.