AbstractCrystallization of atomically precise nanoclusters is gaining increasing attention, due to the opportunity of elucidating both intracluster and intercluster packing modes, and exploiting the functionality of the resulting highly pure crystallized materials. Herein, we report the design and single-crystal X-ray structure of a superfluorinated 20 kDa gold nanocluster, with an Au₂₅ core coated by a shell of multi-branched highly fluorinated thiols (SF₂₇) resulting in almost 500 fluorine atoms, i.e., ([Au₂₅(SF₂₇)₁₈]⁰). The cluster shows a switchable solubility in the fluorous phase. X-ray analysis and computational studies reveal the key role of both intracluster and intercluster F···F contacts in driving [Au₂₅(SF₂₇)₁₈]⁰ crystal packing and stabilization, highlighting the ability of multi-branched fluorinated thiols to endow atomically precise nanoclusters with remarkable crystallogenic behavior.