The gradual evolution from cluster rearrangement to solvation dynamics is discussed by considering the rearrangement of n (n = 1, ..., 19) Ar atoms around Na+-benzene clusters and using an atom-bond potential energy surface. The nature of the bonding is discussed on the basis of the decomposition of the interaction energy and of the formation of the possible conformers. The benzene molecule is found to remain strongly bound to Na+ independently of the number of solvating rare-gas atoms, although due to the anisotropy of the interaction potential, the Ar atoms solvate the Na+-benzene cluster preferentially on the side of the cation. Other specific features of the solvation process are discussed.