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To increase the co-firing ratio of biomass in existing pulverized coal-fired power plants, biomass should be pulverized to obtain a particle size suitable for combustion. However, evaluation of the particle size distribution of each coal and biomass mixture via traditional fuel analysis is difficult. Because coal does not contain neutral sugars, the particle size distribution of biomass in the mixture can be estimated based on its neutral sugar content. The current study was conducted to evaluate the effect of biomass carbonization on the grinding process via neutral sugar analysis. Mixtures of coal and carbonized pine chips with three different degrees of carbonization were prepared and ground using a Hardgrove grindability index mill. In the pulverized mixtures of low carbonized biomass and coal, the biomass content at all particle size ranges was nearly the same as that of the input feedstock. As the degree of biomass carbonization increased, the biomass content in the mixture of large particle sizes was decreased, whereas it was increased in the mixture of small particle sizes. The current study indicated that particle size distribution of coal and biomass in the pulverized mixture depends on the degree of carbonization of biomass.