Addressed herein is a novel, eco-friendly, recoverable, reusable and bottleable catalytic system developed for the dihydroxylation of various olefins yielding 1,2-cis-diols. In our protocol, zeolite-confined osmium(0) nanoclusters (zeolite-Os⁰) are used as reusable catalyst and H₂O₂ served as a co-oxidant. Zeolite-Os⁰ are found to be highly efficient and selective catalysts for the dihydroxylation of a wide range olefins in an aqueous acetone mixture at room temperature. In all of the olefins surveyed, the catalytic dihydroxylation reaction proceeds smoothly and the corresponding 1,2-cis-diols are obtained in excellent chemical yield under the optimized conditions. The present heterogeneous catalyst system provides many advantages, such as being eco-friendly and industrially applicable over the traditional homogenous OsO₄–NMO system for the dihydroxylation of olefins.