Atomically precise gold nanoclusters protected by ligands are being intensely investigated in current catalysis science, due to the definitive correlation between the catalytic properties and structures at an atomic level. By solving the crystal structures of the nanoclusters, coupled with in situ and ex situ spectroscopy, a very fundamental understanding can be achieved to learn what controls the catalytic activation, active site structure, and catalytic mechanism. Herein, we mainly focus on the recent progress in catalysis controlled by precisely modulating the surface structures of the nanoclusters, including the alteration of the surface motifs, the doping of heterogeneous atoms in the surface of the nanoclusters, and the surface ligand engineering. The article is expected to help not only gain deep insight into the crucial roles of surface motifs of the nanoclusters in regulating the catalytic properties, but also explore the wide catalytic applications of atomically precise nanoclusters by elaborately tailoring the surface of the nanoclusters.