Provided is a process for preparing bicyclo[2.2.2]octane-1,4-diol starting from cyclohexane-1,4-dione. The dione is reacted with certain trialkylsilyl halides or trimethylsilyl trifluormethanesulfonate in the presence of a non-nucleophilic base to afford a silyl-substituted diene, which is in turn reacted with ethylene and subsequently reduced to provide the title compound.