We report two novel homoleptic alkynyl-protected gold nanoclusters, which were synthesized by direct reduction of AuCCR. Single-crystal X-ray structural analysis reveals that they have compositions of Au42(CCC6H4-2-CF3)22 (1) and Au50(CC6H4-3-F)26 (2), respectively. Cluster 2 is the first Au50 nanocluster, and the metal-to-ligand ratios of 1 and 2 are different from those of known Aun(SR)m or Aux(CCR)y nanoclusters. In addition, the metal kernels of these two clusters are built up unprecedented units. This work offers further insights into the synthesis of all-alkynyl-protected gold nanoclusters via a direct reduction method.