Abstract 1,4‐Diazabicyclo[2.2.2]octane (DABCO) was found to be an effective reagent for decarboxylative acylation of carboxylic acids with carbamic chlorides or alkyl carbonochloridates. In the absence of a metal catalyst, carboxylic acids such as α‐ketocarboxylic, cinnamic and arylpropiolic acids, underwent the decarboxylative acylation smoothly to afford various α‐keto (or α,β‐unsaturated) amides and esters in good to excellent yields.