A process is disclosed in which optically active glycols are produced through an electrolytic asymmetric dihydroxylation (ADH) reaction involving olefins as substrates. The ADH reaction is mediated by a catalytically active amount of osmium tetroxide or osmium-containing precursor in a protic medium in the presence of chiral ligand. Any lower valent osmium species produced in the course of the ADH reaction is regenerated electrolytically either directly in the absence of a secondary oxidant or indirectly in the presence of a secondary oxidant that itself undergoes electrolytic regeneration.