During combustion of solid fuels in the material inlet end of cement rotary kilns, local reducing conditions can occur and cause decomposition of sulfates from cement raw materials. Decomposition of sulfates is problematic because it increases the gas-phase SO2 concentration, which may cause deposit formation in the kiln system. SO2 release from cement raw materials during combustion of solid fuels has been studied experimentally in a high temperature rotary drum. The fuels were tire rubber, pine wood, petcoke, sewage sludge, and polypropylene. The SO2 release from the raw materials was observed to increase when (a) the inlet oxygen concentration decreased, (b) the temperature increased, and (c) when the total surface area of the fuel particles increased. The type of fuel also had a significant effect on the SO2 release. The sequence of SO2 release for fuel particles in the size interval 1–2 mm was found to be tire rubber granulate > sewage sludge > pine wood sawdust > petcoke > polypropylene flakes. The SO2 release was generally observed to increase when formation of local reducing conditions near the raw material bed increased, as indicated by elevated levels of CO during the fuel devolatilization.