A fluidized bed in situ cell is used to examine the chromia on alumina catalyst surface. The loading is varied from 1 to 20% chromium oxide on alumina. The structure of the surface is monitored as a function of temperature, reduction, and hydration. This is the first study to use ultraviolet excitation to study a reduced chromium catalyst surface. Reduction of the sample in hydrogen gas leads to the formation of noncrystalline Cr3+ species. Addition of potassium to the surface reduces the size of the chromia clusters.