We consider the space of countable structures with fixed underlying set in a given countable language. We show that the number of ergodic probability measures on this space that are S∞-invariant and concentrated on a single isomorphism class must be zero, or one, or continuum. Further, such an isomorphism class admits a unique S∞-invariant probability measure precisely when the structure is highly homogeneous; by a result of Peter J. Cameron, these are the structures that are interdefinable with one of the five reducts of the rational linear order (Q,<).