In strive to lower the energy conversion cost and CO2 net emission, more complex biofuels are used. The combustion of these fuels often creates aggressive and problematic fireside environments in boilers, resulting in reduced availability, which, in turn, may lead to increased usage of fossil fuel in backup boilers. The objective of the present work was to contribute to the efforts of maximizing the availability of a 50 MWth circulating fluidized-bed (CFB) boiler firing complex fuels with high amounts of P, Ca, S, Cl, N, K, and Na. In the present work, ash and deposit samples collected from the flue gas system of a CFB boiler were further analyzed with X-ray powder diffraction, complementing earlier analysis made on the same sample set with scanning electron microscopy equipped with energy-dispersive spectrometry. Thermodynamic calculations were also made. The results clarify details about the ash speciation and transformation as well as effects on boiler operation. A suggestion of a control strategy to minimize corrosion rates in superheaters and SO2 emission to downstream cleaning equipment in full-scale industrial boilers is made. An equation for rough estimation of fuel mix corrosion tendencies is also presented.