The proper understanding and description of the spatial distributions of volatile species is important to the circulating fluidized bed (CFB) reactor design and modeling. Aiming at this issue, a mathematical model has been developed in the present work, which constitutes of two main modules that are validated by experiments, one-dimensional fluid dynamic model and single fuel particle devolatilization model. The simulation of a 135 MWe CFB boiler was conducted. Results show that all volatile species exhibit in general a vertical release profile of bimodal shape (coal inlet area and bottom dense bed) while with quantitative differences, which is mainly attributed to the wide size range of feeding fuel. Compared to the influence of bed temperature, the effect of feeding coal size on the volatile nitrogen release is more obvious. This model can be applied as the devolatilization sub-model for the integral combustion simulation of a CFB boiler.