An efficient Ph₃PAuCl/AgOTf-catalyzed double hydroarylation of alkynes with heteroarenes was developed. Functional alkynes undergo double addition with simple heteroarenes such as pyrroles, furans and thiophenes under mild reaction conditions. The corresponding double-adduct products with nearly 100% regioselectivities were obtained in moderate to high yields. The mechanism of the reaction is also discussed in this paper.