Gold(I) complexes are the catalysts of choice for the selective activation of alkynes in the presence of other unsaturated functional groups. In this Account, we present the development of gold(I)-catalyzed intermolecular reactions of terminal alkynes with functionalized alkenes. In particular, we focus on the synthesis of cyclobutenes by asymmetric gold(I)-catalyzed [2+2] cycloaddition and its applications.