The reaction of gaseous KOH with kaolin and mullite powder under suspension-fired conditions was studied by entrained flow reactor (EFR) experiments. A water-based slurry containing kaolin/mullite and KOH was fed into the reactor and the reacted solid samples were analyzed to quantify the K-capture level. The effect of reaction temperature,K-concentration in the flue gas, and, thereby, molar ratio of K/(Al+Si) in reactants, gas residence time, and solid particle size on K-capture reaction was systematically investigated. Corresponding equilibrium calculations were conducted with FactSage 7.0. The experimental results showed that kaolin reached almost full conversion to K-aluminosilicates under suspension-fired conditions at 1100–1450 °C for a residence time of 1.2 s and a particle size of D50 = 5.47 μm. The amount of potassium captured by kaolin generally followed the equilibrium at temperatures above 1100°C, but lower conversion was observed at 800 and 900 °C. Crystalline kaliophilite (KAlSiO4) was formed at higher temperatures (1300 and 1450 °C), whereas, amorphous K-aluminosilicate was formed at lower temperatures. Coarse kaolin (D50 = 13.48 μm) captured KOH less effectively than normal (D50 = 5.47 μm) and fine(D50 = 3.51 μm) kaolin powder at1100 and 1300 °C. The difference was less significant at 900°C. Mullite generated from kaolin captured KOH less effectively than kaolin at temperatures below 1100 °C. However, at 1300 and1450 °C, the amount of potassium captured by mullite became comparable to that of kaolin.