This work presents a methodology that combines experimental measurements and Computational Fluid Dynamics (CFD) modeling to determine the global reaction kinetics of high heating rate biomass devolatilization. Three particle size ranges of woody biomass are analyzed: small (SF), medium (MF) and large (LF) fractions. Devolatilization mass loss is measured for each fraction in a laminar Drop-Tube Reactor (DTR) in nitrogen atmosphere, using two nominal reactor temperatures of 873 and 1173 K. Single First Order Reaction (SFOR) kinetics are determined by coupling an optimization routine with CFD models of the DTR. The global pre-exponential factors and activation energies for the SF, MF and LF particles are 5880 1/s and 42.7 kJ/mol, 48.1 1/s and 20.2 kJ/mol, and 102 1/s and 24.8 kJ/mol, respectively. These parameters are optimized for the isothermal heat transfer model available in CFD programs, and it is recommended that the specific heat capacity that was used in the optimization (1500 J/kgK) is used together with the parameters. Using the SF kinetics for small wood particles and either of the MF or LF kinetics for large particles, it is expected that more accurate devolatilization predictions can be obtained for the whole fuel size distribution in large scale CFD simulations.