Microstructural analysis of the composite matrix is necessary to understand the performance of the part and its long-term durability. This chapter focuses on the microstructural analysis of engineering thermoplastic-matrix composites and the influence of cooling rate and nucleation on the formation of spherulites in high-temperature thermoplastic-matrix carbon-fiber-reinforced composites. It also describes the microstructural analysis of a bio-based thermosetting-matrix natural fiber composite system.