Hydrated Calcium Aluminate Cement (CAC) is known to have a complex microstructure involving different phase assemblages strongly dependant on the temperature. This work presents an experimental approach to study the microstructure of CAC pastes from the first minute of hydration with controlled time-temperature histories up to several months of curing. The self heating usually occurring in the CAC concrete is considered and its influence on the growth and assemblage of the hydration products and subsequent space filling is shown. Quantification of the degree of CA hydration by BSE image analysis is used to understand the evolution of phases throughout the hydration process. Lithium sulphate is commonly used to control the setting time of CAC based materials. It is shown that this promotes the formation of more stable hydrates, but slightly reduces the extent of CA hydration. (C) 2010 Elsevier Ltd. All rights reserved.