Can achiral organocatalysts linked to chiral polyanionic metal-oxide clusters provide good selectivity in enantioselective CC bond formations? We herein answer this question by disclosing a new active hybrid polyoxometalate-based catalyst for asymmetric Diels-Alder reaction. Chirality transfer from the chiral anionic polyoxometalate to the covalently linked achiral imidazolidinone allows us to obtain Diels-Alder cycloaddition products with good yields and high enantioselectivities using cyclopentadiene and acrylaldehydes as partners.