Reductive ring-opening of epoxides is a green pathway for synthesizing highly value-added alcohols. In this study, we present a practically applicable approach for the synthesis of anti-Markovnikov-type alcohols with high yields from aliphatic and aromatic epoxides under mild conditions by developing porous metal silicate (PMS) catalysts. A PMS material PMS-20 consists of cobalt and nickel bimetal redox-active sites, exhibiting exceptional catalytic activity and selectivity in the reductive ring-opening of terminal epoxides with >99% yield of primary alcohols. Comparing with the existing methods using noble metals, PMS-20 exhibits broad substrate scope and excellent functional group tolerance by synergistic work between cobalt and nickel species, which is clarified by dual chamber cell system characterization and theoretical calculation results.