The present invention relates to a process for preparing 3,4-dialkoxythiophenes or 3,4-alkylenedioxythiophenes in high yield via the rapid decarboxylation of 3,4-dialkoxythiophenedicarboxylic acid or 3,4-aklylenedioxythiophenedicarboxylic acid in a water-miscible polar solvent in the presence of copper catalyst under an oxygen atmosphere.