A method is presented for decarboxylative alkoxy-alkoxycarbonylation of various alkenes with alcohols by electrochemical anodic oxidation of monopotassium ethyloxalate salts with good functional group compatibility. The reaction involves anodic oxidation to form an acyl radical, followed by addition to an olefin to yield a new alkyl radical, which is anodically oxidized to a carbon cation and captured by alcohols to afford β-alkoxyalkanoates. Adding catalytic amounts of ammonium iodide enhanced the efficiency of the reactions.