An alternative to the Lindlar catalyst for the semihydrogenation reaction of alkynes to alkenes is of high interest. Here we show that palladium on carbon (Pd/C), i.e., a widely available supported Pd catalyst, is converted from an unselective to a chemoselective catalyst during the semihydrogenation reaction of alkynes, after the addition of catalytic amounts of commercially available electron-poor phosphines. The catalytic activity is ≤7 times greater, and the selectivity is comparable to that of the industrial benchmark Lindlar catalyst.