<p>Chromium chemistry is attractive to researchers due to its interesting structural arrangements and unusual Cr–Cr bonding interactions. However, the exploration of polymeric Cr_<i>n</i> (<i>n</i> &gt; 3) clusters is challenging because of the difficulty in achieving precise matching between the metal cores and ligands. To the best of our knowledge, planar Cr_<i>n</i> configurations beyond the Cr₃ triangle have not been identified. In this study, we successfully isolated and characterized a Cr₅ cluster using the Zintl ion synthesis route. This cluster exists within the ternary anion [Cr₅Sn₂Sb₂₀]⁴⁻ and the nanoscale dimer fusion anion [(Cr₅)₂Sn₆Sb₃₀]⁶⁻. Furthermore, we elucidated the aromatic properties of the Cr₅Sn₂ subunits through theoretical computational analysis, this aromaticity substantially enhancing the intrinsic stability of these Cr₅ cluster species.</p><p></p>