Pyrolytic characteristics of biomass/coal mixtures were investigated under conditions pertinent to pulverised fuel boilers. It was found that the mixtures of biomass/coal follow the behaviour of their parent materials in an additive manner. The two fuels did not chemically interact under inert conditions indicating a general lack of synergistic effects. As such, the yield of the major pyrolysis products is linearly proportional to the percentage of biomass and coal in the mixture. Even the compositions of the gaseous products from blended samples are linearly proportional to those of their parent fuels. These findings can potentially help to understand and predict the behaviour of biomass/coal blends in practical systems.