Pd/ZrO2 and alkali metal doped Pd/M/ZrO2 catalysts were prepared by incipient-wetness impregnation with ZrO2 from Zr(OH)4 calcination as the support. These catalysts were applied to the selective hydrogenation of 1,4-butynediol (BYD) to 1,4-butenediol (BED). The structures and properties of the catalysts were characterized by BET, XRD, CO2-TPD, XPS, and TEM. The effects of reaction atmosphere and alkali metal dopant on the activity, selectivity and stability of the catalysts in hydrogenation of BYD to BED were investigated. 1.0% Pd/ZrO2 exhibited high catalytic activity (0.048 molBYD/(gPd·s)) and reasonable selectivity of BED (xBYD≈100%，SBED=91.2%) under the conditions of 50 ℃, 2.40 MPa H2 pressure. The presence of ammonia into the reaction mixture inhibits the hydrogenation activity but improves the selectivity of BED. 95.6% selectivity of BED was achieved with complete conversion of BYD. The doping of alkali metals (Li, Na, K, Rb, Cs) onto ZrO2 support improves the selectivity of BED, and Rb is the most effective dopant with BED selectivity up to 94.1%.