Thermoset polymers and composites are lightweight materials extensively used in many industries from aerospace to automotive to prosthetics due to their excellent specific mechanical properties and high chemical resistance. However, these products are conventionally manufactured by labor-intensive processes using subtractive manufactured tooling or molds followed by thermal curing inside an oven or autoclave at elevated temperatures for several hours. Hence, conventional manufacturing approaches are energy- and time-consuming and require expensive equipment. Moreover, lack of design flexibility and poor repeatability are additional challenges, which limit the structural and functional capabilities of such products. In this dissertation, I present a novel approach to address the existing limitations in manufacturing thermosets and their composites by developing rapid curing resin systems and integrating them in additive manufacturing (AM) processes. In the first chapter, state-of-the-art manufacturing methods are reviewed and frontal polymerization (FP) as a promising curing strategy for rapid and energy-efficient manufacturing of thermosets and composites is introduced. In the second chapter, the effect of ambient conditioning and resin chemistry on thermal frontal polymerization of a high-performance resin system is explored. In the third chapter, FP is used to demonstrate, for the first time, simultaneous printing and curing of short carbon fiber-reinforced composites for high performance applications. In the following chapter, AM of a soft and stretchable elastomer with tunable thermomechanical properties manufactured via FP is discussed. In the fifth chapter, the printing process is further improved using an external localized heat source, instead of relying on the exothermic heat of polymerization of the resin, to accelerate the curing rate and make the printing process more robust and applicable to the manufacture of large-scale components. Finally in the last chapter, bubble-free frontal polymerization of polyacrylates is introduced for the developed 3D printing process.