Silicone materials are widely used, from daily life to the military industry. With the advancement of science and technology and the increasing demands of industry, the requirement for high-performance precise structural silicone materials has increased. Therefore, the most important aspect in this field is finding a breakthrough in the synthetic methods. In this review, the latest research developments in controllable morphological structure and composite structure optimized synthesis of silicone materials using the Piers–Rubinsztajn (PR) reaction are summarized. The advantages of the PR reaction compared with traditional synthetic routes to silicone materials are presented. The highly controllable spatial structure of silicone materials and the structural combination of biomass or inorganic materials with silicone materials results in an improvement in performance or function. The morphological control of more complex silicone materials and the synthesis of non-traditional silicone materials with composite structures through the PR reaction will be the main research directions for the development of silicone materials in the future.