Non-classical crystallization, where crystals grow by the building blocks of nanoparticles, has become a significant issue not only in solution but also in the gas phase synthesis such as chemical vapor deposition (CVD). Recently, non-classical crystallization was observed in solution in-situ by transmission electron microscope (TEM) using a liquid cell technique. In various CVD processes, the generation of charged nanoparticles (CNPs) in the gas phase has been persistently reported. Many evidences supporting these CNPs to be the building blocks of thin films and nanostructures were reported. According to non-classical crystallization, many thin films and nanostructures which had been believed to grow by individual atoms or molecules turned out to grow by the building blocks of CNPs. The purpose of this paper is to review the development and the main results of non-classical crystallization in the CVD process. The concept of non-classical crystallization is briefly described. Further, it will be shown that the puzzling phenomenon of simultaneous diamond deposition and graphite etching, which violates the second law of thermodynamics when approached by classical crystallization, can be approached successfully by nonclassical crystallization. Then, various aspects of non-classical crystallization in the growth of thin films and nanostructures by CVD will be described.