A growing interest has been observed for the use of cereal grains in small- and medium-scale heating. Previous studies have been performed to determine the fuel quality of various cereal grains for combustion purposes. The present investigation was undertaken in order to elucidate the potential abatement of low-temperature corrosion and deposits formation by using fuel additives (calcite and kaolin) during combustion of oat. Special emphasis was put on understanding the role of slag and bottom ash composition on the volatilization of species responsible for fouling and emission of fine particles and acid gases. The ash fractions were analyzed with scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), for elemental composition, and with X-ray diffraction (XRD) for identification of crystalline phases. The previously reported K and Si capturing effects of kaolin additive were observed also in the present study using P-rich biomass fuels. That is, the prerequisites for the formation of low melting K-rich silicates were reduced. The result of using kaolin additive on the bottom ash was that no slag was formed. The effect of the kaolin additive on the formation of submicrometer flue gas particles was an increased share of condensed K-phosphates at the expense of K-sulfate and KCl. The latter phase was almost completely absent in the particulate matter. Consequently, the levels of HCl and SO2 in the flue gases increased somewhat. The addition of both calcite assortments increased the amount of formed slag, although to a considerably higher extent for the precipitated calcite. P was captured to a higher degree in the bottom ash, compared to the combustion of pure oat. The effect of the calcite additives on the fine particle emissions in the flue gases was that the share of K-phosphate decreased considerably, while the content of K-sulfate and KCl increased. Consequently, also the flue-gas levels of acidic HCl and SO2 decreased. This implies that the low-temperature corrosion observed in small-scale combustion of oat possibly can be abated by employing calcite additives. Alternatively, if problems with slagging and deposition of corrosive matter at heat convection surfaces are to be avoided, kaolin additive can be utilized, on the condition that the higher concentrations of acidic gases can be tolerated.