Catalytic acylation of nitriles with esters in the presence of 10 mol% NdNa8(OtBu)10(OH) is developed.The procedure is suitable for both enolizable and nonenolizable esters and affords β-ketonitriles in moderate to high yields.The heterometallic alkoxide cluster NdNa8(OtBu)10(OH) is structurally characterized by X-ray diffraction,and a mechanism for the production of β-ketonitriles using the cluster is proposed and verified. Catalytic acylation of nitriles with esters in the presence of 10 mol% NdNa8 (OtBu) 10 (OH) is developed. The procedure is suitable for both enolizable and nonenolizable esters and affords β-ketonitriles in moderate to high yields.The heterometallic alkoxide cluster NdNa8 (OtBu) 10 (OH) is structurally characterized by X-ray diffraction, and a mechanism for the production of β-ketonitriles using the cluster is proposed and verified.