Ultrafine nanoclusters with precise structure as catalysts are of particular interest due to high sites density, high metal atomic efficiency and potentially favorable metal-support interactions. In this work, we used a simple wet impregnation method to fix three Cu n (n = 3, 6, 11) nanoclusters (NCs) on activated carbon (AC). The structural characteristics of the three obtained Cu n (n = 3, 6, 11)/AC catalysts were analyzed by FT-IR, XRD, TEM and XPS. Cu n (n = 3, 6, 11)/AC catalysts are used for exploring catalytic performance of alkyne-haloalkane-amine (AHA) coupling reaction. The results show that Cu n (n = 3, 6, 11)/AC catalysts exhibited better catalytic activity for AHA coupling reaction than Cu salt and other non-noble metal catalysts, with TON up to 715.4. This work provides a new way to understand the relationship between structure and catalytic performance of ultra-small copper NCs.