A novel system is described for monitoring rapid changes in particle size and temperature during coal devolatilization at heating rates representative of high-intensity combustion environments. The system incorporates an electrodynamic balance and a pulsed radiation source to isolate and rapidly heat individual particles. A high-speed two-dimensional photodiode array and a single wavelength radiation pyrometer are applied to record changes in particle size and temperature. Dynamics of volatile evolution and particle swelling are also recorded using high-speed cinematography. Measurements of temperature and size changes are reported for carbon spheres and a HVA bituminous coal at heating rates on the order of 10 5 K/s. Measured temperature histories are compared with theoretical estimates of the temperature response of radiatively heated coal and carbon particles. The analysis considers the development of the transient temperature distribution inside the particles by numerical solution of the Fourier equation. Measurements and model predictions for 135-μm-diameter carbon spheres were in excellent agreement using property data correlations commonly applied in modeling coal devolatilization and combustion behavior. Model predictions for coal particles, however, significantly underestimated (on the order of 50%) the observed heating rates for 115-μm-diameter coal particles using the same property correlations. It is concluded that coal particles heat significantly faster than is predicted using commonly employed approaches to model heat transfer with assumptions routinely applied to coal. Potential reasons for this may include inadequate understanding of relevant coal thermodynamic and heat transfer properties as well as failure to account for particle shape factors. Heat transfer analyses employing spherical particle assumptions and commonly used coal property correlations can lead to large errors in predicted temperature histories and associated devolatilization rates.