AbstractIntermolecular interactions involving aromatic rings are ubiquitous in biochemistry and they govern the properties of many organic materials. Nevertheless, our understanding of the structures and dynamics of aromatic clusters remains incomplete, in particular for systems beyond the dimers, despite their high presence in many macromolecular systems such as DNA and proteins. Here, we study the fragmentation dynamics of benzene trimer that represents a prototype of higher-order aromatic clusters. The trimers are initially ionized by electron-collision with the creation of a deep-lying carbon 2s⁻¹ state or one outer-valence and one inner-valence vacancies at two separate molecules. The system can thus relax via ultrafast intermolecular decay mechanisms, leading to the formation of C${}_{6}{{{{{{{{{\rm{H}}}}}}}}}_{6}}^{+}⋅$ 6 H 6 + ⋅ C${}_{6}{{{{{{{{{\rm{H}}}}}}}}}_{6}}^{+}⋅$ 6 H 6 + ⋅ C${}_{6}{{{{{{{{{\rm{H}}}}}}}}}_{6}}^{+}$ 6 H 6 + trications and followed by a concerted three-body Coulomb explosion. Triple-coincidence ion momentum spectroscopy, accompanied by ab-initio calculations and further supported by strong-field laser experiments, allows us to elucidate the details on the fragmentation dynamics of benzene trimers.