An efficient and highly selective heterogeneous catalyst system for hydroamination of alkynes was developed using unsupported gold nanopores (AuNPore) for the first time. The AuNPore-catalyzed highly regioselective hydroamination of alkynes proceeded smoothly without any additive and solvent under mild conditions (rt-50 °C) to yield Markovnikov imines in satisfactory to excellent yields. No gold leached from AuNPore during the hydroamination of alkynes. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. A one-pot, two-step procedure using a single AuNPore catalyst has been devised to produce secondary amines derived from readily available alkynes and anilines with high atom efficiency.