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As a novel family of 2D materials, MXenes have drawn intensive interests owing to its fascinating property profile. The ability to grow high‐quality MXenes in a controllable way would in turn further promote the development of fabrication techniques and expand wide advanced applications. Then 2D MXenes crystals are highly desirable and many approaches have been explored to realize the mass production. Chemical vapor deposition (CVD) provides compelling benefits over other alternatives in controllability, uniformity and scalability. In this review, the recent advances in growth of MXenes crystals by CVD method will comprehensively present. Several typical kinds of MXenes crystals are demonstrated to be fabricated with a precise control in terms of size, morphology and thickness. Further, a series of MXenes heterostructures are constructed including vertical and lateral spatial orientations. Then, the properties and applications of MXenes crystals are exhibited, of which superconductivity and electrochemical catalysts will be mainly emphasized. Finally, the authors put forward views on the future development in the synthesis of MXenes. With continuous efforts devoted, a bright future of MXenes crystals prepared by CVD is expected. [ABSTRACT FROM AUTHOR]