A one-pot, regioselective decarboxylative alkynylation of tetrahydro-β-carboline-1-carboxylic acid under peroxide-free condition is reported. The reaction is highly selective for the 1-position over the 3-position of tetrahydro-β-carboline. The reaction can afford alkynylated or enaminone products depending on the reagent. The reaction proceeds through sequential decarboxylative iminium ion formation followed by an alkynylation and oxidative rearrangement cascade.