Density functional theory calculations have been performed to study the experimentally synthesized Au₃₀S(SR)₁₈ and two related Au₃₀(SR)₁₈ and Au₃₀S₂(SR)₁₈ clusters. The patterns of thiolate ligands on the gold cores for the three thiolate-protected Au₃₀ nanoclusters are on the basis of the “divide and protect” concept. A novel extended protecting motif with u₃-S, S(Au₂(SR)₂)₂AuSR, is discovered, which is termed the tridentate protecting motif. The Au cores of Au₃₀S(SR)₁₈, Au₃₀(SR)₁₈ and Au₃₀S₂(SR)₁₈ clusters are Au₁₇, Au₂₀ and Au₁₄, respectively. The superatom-network (SAN) model and the superatom complex (SAC) model are used to explain the chemical bonding patterns, which are verified by chemical bonding analysis based on the adaptive natural density partitioning (AdNDP) method and aromatic analysis on the basis of the nucleus-independent chemical shift (NICS) method. The Au₁₇ core of the Au₃₀S(SR)₁₈ cluster can be viewed as a SAN of one Au₆ superatom and four Au₄ superatoms. The shape of the Au₆ core is identical to that revealed in the recently synthesized Au₁₈(SR)₁₄ cluster. The Au₂₀ core of the Au₃₀(SR)₁₈ cluster can be viewed as a SAN of two Au₆ superatoms and four Au₄ superatoms. The Au₁₄ core of Au₃₀S₂(SR)₁₈ can be regarded as a SAN of two pairs of two vertex-sharing Au₄ superatoms. Meanwhile, the Au₁₄ core is an 8e-superatom with 1S²1P⁶ configuration. Our work may aid understanding and give new insights into the chemical synthesis of thiolate-protected Au clusters.