Abstract The Ru-catalyzed highly selective alkoxycarbonylation of allenes with aliphatic alcohols allow to produce useful α , β -unsaturated esters in good to excellent yields under mild condition (temperature is 70 o C). Efficient regioselectivity could be controlled in the presence of N-ligands while the P-ligands had no influence on the conversion of substrates and the chemo/regioselectivity of target products. By involving N-ligand (4,7-dimethyl-1,10-phenanthroline, N9 ) in the catalytic system, α , β -unsaturated esters were obtained with high conversion and chemo/regioselectivity (Conversion up to 99 %, chemical selectivity up to 99 %, regioselectivity of branched ester/linear ester up to 89/11).