It has been surprisingly discovered in accordance with the present invention that when 1,3-dioxolane is reacted with formaldehyde in the presence of tert-butyl hydroperoxide and a cobalt initiator, the reaction preferentially involves an addition of the formaldehyde to the 2-methylene group of the 1,3-dioxolane with only minor reaction with the 4-methylene and 5-methylene groups of the 1,3-dioxolane whereby the reaction product that is formed contains significant quantities of 2-hydroxyalkyl-1,3-dioxolanes and only minimal amounts of the undesired methyl formate by-product. 2-Hydroxymethyl-1,3-dioxolane is hydrolyzed with comparative ease to ethylene glycol and the corresponding glycol aldehyde (CHO--CH.sub.2 --OH). The glycol aldehyde in turn can be catalytically hydrogenated to form additional quantities of ethylene glycol.