Understanding the precipitation reaction is very important since precipitation hardening is one of the most effective strengthening mechanisms in metallic alloys. In martensitic steels, a tempering heat treatment is often performed. During tempering various new phases are precipitated and the spatial and temporal evolution of these precipitates strongly influences the properties of the steel, such as strength/ductility, creep, fatigue and hot corrosion resistance. Therefore, the possibility of quantitative modelling of the precipitation process will provide many opportunities for advanced materials and process design and optimization as well as service life assessments. The Fe-C-Cr system forms the basis for tool steels and is consequently used in many applications such as e.g. metal forming operations. They are characterized by a high hardness and good toughness, even at elevated temperatures.In the present work, the as-quenched martensitic microstructures of four Fe-C-Cr alloys with varying Cr and C contents were characterized by Light Optical Microscopy (LOM) and Electron Microscopy. The effects of Cr and C on the morphology of martensite were investigated. It was found that Cr addition had a similar effect as C on the martensitic morphology and on the ratio of high-angle grain boundary (HAGB) to low-angle grain boundary (LAGB). However, the micro-hardness was unaffected by the Cr addition whilst it was strongly influenced by the C addition.In addition, a quantitative experimental characterization of the precipitates formed during tempering of the martensite was performed. The Langer-Schwartz theory combined with the Kampmann-Wagner-Numerical (KWN) method, as implemented in the software TC-PRISMA, was used to predict the precipitation of carbides after tempering in one of the model alloys: Fe-0.15C-4.0Cr (mass%). The microstructure characterization of the as-quenched material provided vital input parameters for the modelling work and a comparison was made between the modelling predictions and the experimental results. The effect of parameters such as dislocation density, grain size and interfacial energy on the precipitation of carbides was discussed.