Sublimation crystallization, a solvent-free purification technique, has emerged as a sustainable strategy in materials science for producing high-purity substances and advanced functional materials. This review delves into the thermodynamic and kinetic principles governing sublimation crystallization, such as vapor pressure, temperature, and molecular interactions, which play crucial roles in phase transitions and crystal growth. We then explore its practical applications in the separation and purification of materials, the preparation of high-quality single crystals, polymorph and cocrystal screening, and the fabrication of thin films and semiconductor devices. By clarifying the processes and mechanisms involved, this review aims to provide insights into how sublimation crystallization optimizes separation and purification techniques while enhancing material properties as a secondary benefit. This work also outlines future directions and challenges for refining high-efficiency purification methods and advancing sustainable chemical engineering technologies.