K₂PtCl₄/Xphos-SO₃Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly regio- and stereoselective catalyst for the hydrosilylation of terminal alkynes with hydrosilanes. The reaction could be conducted under mild conditions, yielding a variety of functionalized β-(E)-vinylsilanes in good to excellent yields with a total β-(E)-selectivity. The isolation of the products is readily performed by extraction with cyclohexane and more importantly, both expensive K₂PtCl₄ and Xphos-SO₃Na in a PEG-400/H₂O system could be easily recycled and reused at least eight times without any loss of catalytic activity.