A methodology is described for characterizing the spatial distribution of thermal mismatch stresses at grain level in B4C-SiC-Si ceramic composites using Raman spectroscopy. Unlike traditional methods to detect residual stresses (e.g., X-ray diffraction) which provide average values of stress over the entire specimen surface, Raman peak-shift analysis provides residual stress distributions within the microstructure at high spatial resolution. While classical formulation predicts uniform compressive stress within a Si-phase surrounded by the ceramic matrix, the Raman measurements revealed non-uniform residual stress distributions in Si when the particle size was larger than 5 microns. For large irregular shaped particles, the two methods coincide only along the interface between the particle and matrix, but vary drastically both in magnitude and nature in the interior of the particle where large tensile stresses have been measured. The presence of anomalous tensile stress in the interior of the minor Si-phase results in defect generation and structural disorder which has been confirmed by TEM analysis. Raman spectroscopic mapping was also used to compute an average macroscale residual stress value for a given material composition allowing links to be drawn between processing, microstructure and properties. The average residual stress within the microstructure was found to correlate well with the estimates based on volume fraction of the constituents and material properties.