The orientations and surface structures of ferroelastic CaTiO3 crystals within a polycrystalline ceramic were measured by electron backscatter diffraction and atomic force microscopy (AFM) respectively. Surfaces annealed at 1250 degrees C in air are made up of a combination of facets with orientations near {100}, {110}, and {111} (indexed with reference to the cubic perovskite cell). The samples were immersed in an aqueous AgNO3 solution and illuminated to photochemically reduce silver. Based on the amount of silver reduced on different surfaces, it was determined that surfaces with a {111} orientation had the greatest photocathodic reactivity, those with a {110} orientation had the least photocathodic reactivity, and surfaces with the {100} orientation had intermediate reactivity. While the {110} surfaces were essentially inert for photocathodic reduction, they were active for the photoanodic oxidation of Mn2+. Ferroelastic domains were observed to enhance and retard the photochemical reduction of silver on spatially alternating domains on 20% of the grains. However, domains had no influence on the reactivity of the other 80% and are therefore secondary to the surface orientation in determining the reactivity.