To examine the influence of calcium on the mechanisms of brown coal pyrolysis and gasification, the morphology of chars from raw and calcium-exchanged YaUourn brown coal was analysed. The chars were obtained by slow pyrolysis in a thermo gravimetric analyser and rapid pyrolysis in fluidized bed reactors operating at atmospheric pressure and at 1.1 MPa. They were examined by optical microscopy to determine reflectance and the percentage of particles that had become plastic during pyrolysis. In addition to confirming calcium's inhibiting effect on tar yield, the results from the rapid pyrolysis experiments show that in the presence of calcium, char reflectivity decreases, char H/C ratio increases, and the proportion of particles going through a plastic stage decreases. Calcium's inhibition of plasticity development is augmented by high pressure in the fluidized bed reactor. The effects appear to be attributable to the action of carboxylate calcium as a cross-linking agent, leading to the formation of a tighter char structure which traps the organic material that would otherwise be liberated as tar. The presence of Ca also increases the H/C ratio of the chars produced by slow pyrolysis, but the mechanism of pyrolysis differs, since in slow pyrolysis none of the particles showed evidence of plasticity. In slow pyrolysis, calcium's influence on char reflectivity depends on the holding temperature, since temperature determines the extents of both coal devolatilization and catalytic transformations. The roles of calcium in these processes and their influence on optical anisotropy and reflectance are discussed.