Abstract Herein we report the systematic exploration of the potential energy surfaces of a series of clusters with formula E 5 M 7 + (E=C‐Pb and M=Li‐Cs). Fifteen of these combinations adopt a D 5 h three‐dimensional seven‐pointed star‐like structure in a singlet state, where M atoms interact electrostatically with the E 5 ring. The determining factors in the relative preference of having the D 5 h structure over the most competitive isomer or vice‐versa are analyzed. These star‐shaped systems satisfy the 4n+2 Hückel's rule and exhibit a strong diatropic (σ and π) response to an external magnetic field.