The objective of the present work is to elucidate the influence of intraparticle mass and heat transfer phenomena on the overall rate and product yields during devolatilization of a single coal particle in an inert atmosphere. To this end a mathematical model has been formulated which covers transient devolatilization kinetics and intraparticle mass and heat transport. Secondary deposition reactions of tarry volatiles also are included. These specific features of the model allow a quantitative assessment to be made of the impact of major process conditions such as the coal particle size, the ambient pressure and the heating rate on the tar, gas and total volatile yield during devolatilization. Model predictions are compared to a limited number of experimental results, both from the present work and from various literature sources.