The palladium-catalyzed regioselective alkoxycarbonylation of allenes with aliphatic alcohols allows to produce synthetically useful alpha,beta- and beta,gamma-unsaturated esters in good yields. Efficient selectivity control is achieved in the presence of appropriate ligands. Using Xantphos as the ligand, beta,gamma-unsaturated esters are produced selectively in good yields. In contrast, the corresponding alpha,beta-unsaturated esters are obtained with high regioselectivity in the presence of PPh2Py as the ligand. Preliminary mechanistic studies revealed that these two catalytic processes proceed by different reaction pathways. In addition, this novel protocol was successfully applied to convert an industrially available bulk chemical, 1,2-butadiene, into dimethyl adipate, which is a valuable feedstock for polymer and plasticizer syntheses, with high yield and TON (turnover number).