Efficient H2O2-based oxidn. systems with three kinds of polyoxometalates, [ホウ-SiW10O34(H2O)2]4- (I), [ホウ-1,2-H2SiV2W10O40]4- (II), and [W2O3(O2)4(H2O)2]2- (III) are reported. I can catalyze epoxidn. of various olefins including non-activated terminal olefins such as propylene and 1-octene with 竕・99% selectivity to epoxide and 竕・99% efficiency of H2O2 utilization. It is notable that II shows unique stereospecificity, regioselectivity, and diastereoselectivity for the epoxidn. of cis/trans olefins, non-conjugated dienes, and 3-substituted cyclohexenes, resp. The epoxidn. of various allylic alcs. with only 1 equiv. H2O2 in water can be efficiently catalyzed by III to give the corresponding epoxy alcs. in high yields. Further, the catalyst III can be recycled with the maintenance of the catalytic performance. [on SciFinder(R)]