In this study, a multi-technique approach was utilised to determine the high temperature performance of magnesium potassium phosphate cement (MKPC) blended with fly ash (FA) or ground granulated blast furnace slag (GBFS) with respect to nuclear waste immobilisation applications. Conceptual fire conditions were employed (up to 1200 degrees C, 30 min) to simulate scenarios that could occur during interim storage, transportation or within a final geological disposal facility. After exposure up to 400 degrees C, the main crystalline phase, struvite-K (MgKPO4.6H(2)O), was dehydrated to poorly crystalline MgKPO4 (with corresponding volumetric and mass changes), with MgKPO4 recrystallisation achieved by 800 degrees C. XRD and SEM/EDX analysis revealed reaction occurred between the MgKPO4 and FA/GBFS components after exposure to 1000-1200 degrees C, with the formation of potassium aluminosilicate phases, leucite and kalsilite (KAlSi2O6 and KAlSiO4), commensurate with a reduced relative intensity (or complete elimination) of the dehydrated struvite-K phase, MgKPO4. This was further supported by solid-state NMR (Al-27 and Si-29 MAS), where only residual features associated with the raw FA/GBFS components were observable at 1200 degrees C. The high temperature phase transformation of blended MKPC binders resulted in the development of a glass/ceramic matrix with all existing porosity infilled via sintering and the formation of a vitreous phase, whilst the physical integrity was retained (no cracking or spalling). This study demonstrates that, based on small-scaled specimens, blended MKPC binders should perform satisfactorily under fire performance parameters relevant to the operation of a geological disposal facility, up to at least 1200 degrees C.