Within the pyrolysis modeling of biomass, the solid is typically interpreted as a mixture of cellulose, hemicellulose, and lignin, where the components react independently before the products are linearly superimposed. This assumption applies to the bio-chemical percolation devolatilization model (Bio-CPD), which, as a network model, represents the physicochemical processes very realistically. A literature review regarding available structural and kinetic parameters for the Bio-CPD model revealed four hits. To investigate and evaluate the model predictivity, experiments from extracted lignocellulosic biomass components pyrolyzed separately in a fluidized bed reactor are used as reference data. Using single-component data simplifies the reaction chemistry by minimizing interactions between the components and best approximates the model assumptions. The comparison between experimentally obtained total volatile release rates and model predictions revealed the parameter set from Vizzini et al. (2008) for cellulose and the one from Sheng and Azevedo (2002) for hemicellulose as best-suitable candidates to predict the pyrolysis behavior for the boundary conditions of the fluidized bed reactor. For lignin, instead, the Genetti correlation (Genetti, Fletcher, and Pugmire, 1999) to estimate structural parameters based on the ultimate and proximate analysis led to better results than all other sets. Further, the analysis of light gas and tar fractions showed a high relevance to model secondary tar cracking reactions in the fluidized bed reactor system.