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A divacant, lacunary, Keggin-type silicotungstate, [γ-SiW 10 O 34 (H 2 O) 2 ] 4- , exhibits high catalytic performance for the epoxidation of various nonconjugated dienes using hydrogen peroxide under mild conditions, high regioselectivity to the more accessible double bonds, and high efficiency of hydrogen peroxide utilization. The high regioselectivity for the [γ-SiW 10 O 34 (H 2 O) 2 ] 4- -catalyzed epoxidation would be caused by the steric hindrance of the active site.