Three-dimensional printing technology provides substantial developmental advantages for silicone rubber, such as enhanced precision, the ability of fabricating intricate structures, and accelerated manufacturing processes. This review first offers an overview of 3D printing technology and its commonly used materials, with a particular emphasis on diverse materials introduced in recent years, especially those suitable for high-performance elastomers such as silicone rubber. It then comprehensively analyzes the characteristics, advantages, and challenges of 3D printed silicone rubber, including its processing adaptability and molding performance. A detailed discussion follows the characterization techniques, including mechanical testing, electron microscopy, thermal analysis, and scattering methods, which are used to evaluate the microstructure, mechanical properties, and thermal stability of the printed materials. Finally, the review explores the application of neutron scattering techniques in studying 3D printed silicone rubber, highlighting how these methods deepen the understanding of the material's microstructure, particularly in terms of polymer chain configuration and molecular dynamics. By integrating the latest advancements, this review aims to serve as a valuable reference for design, optimization, and industrial implementation of 3D printed silicone rubber.