Layered perovskites (Ruddlesden–Popper phases), (CaxSr1−x)n+1 TinO3n+1 with n = 3, ∞ and x ranging from 0 to 1, have been investigated by XPS and XAES. The structural transitions, identified in other studies, have been correlated with changes in the chemical environments of the constituent species. In particular, the tetragonal to orthorhombic transition at x = 0.65 ± 0.1 appears to generate nonequivalent cation environments for the alkaline earth species in (Ca, Sr)O12 coordination. Other binding and kinetic energy shifts can be correlated with changes in and distortions of unit cell volumes.