The encapsulation of polyoxometalates within the large pores of the Zr(iv) biphenyldicarboxylate UiO-67 metal-organic framework has been achieved, for the first time, by direct solvothermal synthesis. The resulting POM@UiO-67 composite materials were fully characterized by XRPD, IR, MAS NMR, N2 porosimetry measurements and cyclic voltammetry.