β-Ketophosphonates are an important class of carbonyl compounds which exhibit a wide range of biological activities and outstanding metal-complexing abilities. They are building blocks in organic synthesis, especially as intermediates for the synthesis of α,β-unsaturated carbonyl compounds, chrial β-hydroxy and β-hydroxy phosphonic acids. In this paper, a simple, convenient and environmentally benign method to synthesize the β-ketophosphonates from alkynylphosphonates was developed, which can be easily prepared in one step from commercial terminal alkynes. In the presence of 2.5 mol% XPhosAuSbF 6 and 3 equiv. of water in dichloroethane at room temperature, a broad range of alkynylphosphonates were converted into the corresponding β-ketophosphonates in nearly equivalent conversion through gold-catalyzed hydration reaction. The presented methodology will provide new strategies for β-ketophosphonates-type natural product and drug synthesis, which has important academic significance and application value.