Vapor-phase catalytic dehydration of 1,4-butanediol (1,4-BDO) was investigated over rare earth metal oxide (RE2O3) catalysts to produce 1,3-butadiene (BD). Among eight RE2O3, Yb2O3 showed the highest catalytic activity to produce BD via an intermediate 3-buten-1-ol (3B1OL). Hydrothermal (HT) aging of precursor precipitate of Yb2O3 greatly enhanced the catalytic activity and the selectivity to 3B1OL of the resulting Yb2O3 catalyst. It was confirmed that the morphology of Yb2O3 and the catalytic activity varied with the HT conditions. Hydrothermally aged Yb2O3 reduced the formation of propylene, a decomposed product of 3B1OL, even at high temperatures above 400 °C. HT-aged Yb2O3 followed by calcination at 700 °C showed excellent catalytic activity in the dehydration of 1,4-BDO with the highest BD productivity of 34.6 mol kgcat−1 h−1 and a high BD yield of 97.4% at 450 °C.