The energy transition from the incineration and gasification of fossil fuels to the incineration and gasification of biomass refractory linings is being held up by a severe corrosion issue, caused by high alkali contents and the wide variety of biomass sources. Incinerators optimized for fossil fuels are commonly lined with mullite, Al2O3-Cr or SiC-based refractory products; however, those materials are not always suitable for the use of organic fuels. Hibonite (CaO·6Al2O3)-based refractory products have shown promising performance because of their high resistance against alkali attacks. Indeed, previous works have shown that the reaction between calcium hexa-aluminate and an alkali does not lead to the strong volume expansion observed with other mineral phases, such as corundum or andalusite. The present work aims to describe the reactions kinetics occurring between hibonite-based raw materials and biomass ashes. Therefore, the three main oxides contained in an average biomass, namely, CaO, SiO2 and K2O, were selected to examine the high temperature reactions with a calcium hexa-aluminate matrix. The resulting phase composition and microstructure were compared with the performance of an alumina matrix through, respectively, X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The post-mortem observations show a higher extent of reaction for the alumina than for the calcium hexa-aluminate. Moreover, the microstructure of the alumina matrix suffered a strong chemical spalling, while the calcium hexa-aluminate microstructure remained undamaged after the corrosion.