The mixing of coal and solid heat carriers on the coal pyrolysis process was studied with a continuous colliding static mixer. A two-dimensional Markov chain model of both single-element and multielement has been developed to describe the mixing process of coal and solid heat carriers on the free surface. Some simulations were presented to investigate the evolution of the mixture state, as well as the influence of the initial distribution and the feeding ratio of the components on the mixing kinetics. Mixing experiments with coal and ceramic balls were carried out to validate the single-element Markov chain model proposed in this work. The experimental results of mixing coal and ceramic balls were in good agreement with those predicted from the model, demonstrating that the model was able to effectively describe the mixing process in the continuous colliding static mixer. The multielement model gave guidance and direction of mixing optimization for the application of the continuous colliding static mixing in large-scale coal pyrolysis industry. The results indicated that the transition matrices depended mainly on the type of mixing elements in a continuous colliding static mixer and had little relation with the property of particles. The present study justified that a continuous colliding static mixer was suitable for mixing binary inhomogeneous particle systems.