Volatile-char interaction is important for the operation of co-gasification of coal and biomass. Biomass generally produces large amount of volatiles while char is mainly produced from coal. Hence, in this study, the interaction between coal char and volatiles from biomass samples (xylan, cellulose and rice straw) was examined using a rapid-heating thermobalance reactor. Three types of coal char, consisting of slow pyrolyzed-coal char (Ex-char), fast pyrolyzed-coal char (In-char), and acid washed-coal char (Ac-char), were employed to reveal influences of heating rate during char preparation and retention of alkali and alkaline earth metallic (AAEM) species on char surface. The steam gasification rates of all coal chars in both cases with and without volatile contacting were investigated from the gas evolution rate and remaining char analyses. The results indicate that the steam gasification rates of Ex-char and In-char were significantly diminished by the volatiles derived from all sources, especially rice straw. However, in the case of Ac-char, the reduction of steam gasification rate was less important Moreover, the Ex-char exhibited the catalyst for the decomposition of biomass volatiles, resulting in the increase in gas production rate. Porous structure and the AAEM over char play crucial roles on the volatile-char interaction. (C) 2013 Elsevier B.V. All rights reserved.