We report the observation of dimerization of two 8‐electron superatom cluster units in the crystallographic structures of Au2Ag42(SAdm)27(BPh4) and [Au2Ag48(S‐tBu)20(Dppm)6Br11]Br(BPh4)2 nanoclusters. The crystallographic analysis reveals that both nanoclusters have a Au2Ag24 core made of two separated icosahedral without sharing metal atoms, and each icosahedron has an eight‐electron (8e) closed shell (1S21P6). The valence electronic structures of these two nanoclusters are analogous to that of a Ne atom dimer (Ne2) according to the density functional theory (DFT) analysis. This is the first crystallographic observation of the dimerization of 8‐electron superatom units. This study enriches the fundamental knowledge on metal superatom clusters and implies the possibility for further assembling metal superatom building blocks into higher order superatom molecules.