The precise location of an ion or electron, whether it is internally solvated or residing on the surface of a water cluster, remains an intriguing question. Subtle differences in the hydrogen bonding network may lead to a preference for one or the other. Here we discuss spectroscopic probes of the structure of gas-phase hydrated ions in combination with quantum chemistry, as well as H/D exchange as a means of structure elucidation. With the help of nanocalorimetry, we look for thermochemical signatures of surface vs internal solvation. Examples of strongly size-dependent reactivity are reviewed which illustrate the influence of surface vs internal solvation on unimolecular rearrangements of the cluster, as well as on the rate and product distribution of ion-molecule reactions.