Novel bioinorganic hybrid materials based on proteins and inorganic clusters have enormous potential for the development of hybrid catalysts that synergistically combine properties of both materials. Here we report the creation of hybrid assemblies between a computationally designed symmetrical protein Pizza6-S and different polyoxometalates with matching symmetry: the tellurotungstic Anderson-Evans (Na₆[TeW₆O₂₄]·22H₂O) (TEW); Keggin (H₄[SiW₁₂O₄₀]·6H₂O) (STA); and 1 : 2 Ce^III-substituted Keggin (K₁₁[Ce^III[PW₁₁O₃₉]₂]·20H₂O) (Ce-K). This results in the formation of complexes with clearly defined stoichiometries in solution. Crystal structures validate the complexes as building blocks for the formation of larger assemblies.