This paper presents a model developed for hot water extraction of birch wood meal. Besides solids, two liquid phases are assumed in the system: liquid bound to a wood fiber wall and the other remaining external liquid. True chemical species, their reactions, and diffusion between the liquid phases are considered in the model. The breakdown of hemicellulose into short-chain polymers and monomeric sugar units is modeled by applying an accurate and computationally efficient population balance approach. State-of-the-art correlations and equations are used, thus aiming for a truly predictive model. Several thermodynamic and kinetic submodels are integrated to achieve additional information compared to models already presented in the literature. The presented model is capable of reproducing the measured concentration profiles of chemical species and molecular weight distribution of hemicellulose polymers as a function of the process conditions. The output concentration data are further utilized to calculate the dissolved species and pH in the two liquid phases. Eventually, it could be utilized in optimizing a batch hot water extraction process to maximize either the yield of long-chain hemicelluloses or their monomeric sugars.