Potassium-fly ash (K-FA) sorbents were investigated for high temperature CO2 sorption. K-FAs were synthetised using coal fly ash as source of silica and aluminium. The synthetised materials were also mixed with Li2CO3 and Ca(OH)2 to evaluate their effect on CO2 capture. Temperature strongly affected the performance of the K-FA sorbents, resulting in a CO2 uptake of 1.45 mmol CO2/g sorbent for K-FA 1:1 at 700°C. The CO2 sorption was enhanced by the presence of Li2CO3 (10 wt%), with the K-FA 1:1 capturing 2.38 mmol CO2/g sorbent at 700°C in 5 min. This sorption was found to be similar to previously developed Li-Na-FA (2.54 mmol/g) and Li-FA (2.4 mmol/g) sorbents. The presence of 10% Li2CO3 also accelerated sorption and desorption. The results suggest that the increased uptake of CO2 and faster reaction rates in presence of K-FA can be ascribed to the formation of K-Li eutectic phase, which favours the diffusion of potassium and CO2 in the material matrix. The cyclic experiments showed that the K-FA materials maintained stable CO2 uptake and reaction rates over 10 cycles.