The C 1s →π* transition in molecular benzene and benzene clusters is investigated by photoion yields at high energy resolution. The vibrationally resolved band shows the same shape in clusters as in the bare molecule, but it is redshifted by 50 meV in small clusters, i.e. near the threshold of cluster formation. This redshift increases to 70 meV with increasing cluster size. The results are assigned in comparison with ab initio calculations on model structures of dimers, trimers, and tetramers. These indicate that different carbon sites in the molecular moieties give rise to distinct spectral shifts, where carbon sites that are pointing to the π-system of another molecule show a larger redshift than the other ones. Such structural properties are found in solid benzene, so that the gas-to-solid shift of C 1s →π* excited benzene is derived to be a redshift which is of the order of 100-180 meV.