This study involves investigating the correlation between variation of internal structure and heating temperature of alkali-activated fire protection materials using fly ash. Dehydration and micro crack thermal expansion occur in cement hydrates of cementitious materials heated by fire. Internal structure difference due to both the dehydration of cement hydrates and pore solution causes and influences changes in the properties of materials. Also, this study is concerned with change in microstructure and dehydration of the alkali-activated fire protection materials at high temperatures. The testing methods of alkali-activated fire protection materials in high temperature properties are make use of TG-DSC and mercury intrusion porosimetry measurements. The study results show that the alkali-activated fire resistant finishing material composed of potassium hydroxide, sodium silicate and fly ash has the high temperature thermal stability. These thermal stability is caused by the ceramic binding capacity induced by alkali activation reaction.