The effect of fuel origin on synergy in coal/biomass blends during co-gasification has been assessed using a congruent-mass thermogravimetry analysis (TGA) method. Results revealed that synergy occurs when ash residuals are formed, followed by an almost complete gasification of biomass. Potassium species in biomass ash play a catalytic role in promoting gasification reactivity of coal char, which is a direct consequence of synergy during co-gasification. The SEM-EDS spectra provided conclusive evidence that the transfer of potassium from biomass to the surface of coal char occurs during co-pyrolysis/gasification. Biomass ash rich in silica eliminated synergy in coal/biomass blends but not to the extent of inhibiting the reaction rate of the blended chars to make it slower than that of separated ones. The best result in terms of synergy was concluded to be the combination of low-ash coal and K-rich biomass. (C) 2015 Elsevier Ltd. All rights reserved.