Benzene dimer is a prototype to study intermolecular interactions between aromatic systems. OWing to the weak interactions between the moledules within the dimer, several conformational geometries are nearly isoenergetic and thus coexist:even at low temperatures, Furthermore, standard Spectroscopies are unable to distinguish between them. In this work, we study the electronic relaxation processes following inner-valence ionization of benzene and the lowest conformers of benzene dither. We show that the kinetic energy distributions of the secondary electrons emitted via two autoionization mechanisms, namely, the Auger and the intermolecular coulombic decay (ICD) effects, provide a means to probe the conformers of benzene dimer. The proposed spectroscopy opens the way to a better characterization of weakly bound molecular clusters.