Tetradymite-type Bi2X3 (X = Se, Te, Sb) systems have been used as the best thermoelectric materials for decades. Recently, such V-VI compound materials have attracted immense interests because they are identified as topological insulators with salient features associated with the unique topological surface states. In this chapter, we review the use of molecular beam epitaxy technique to achieve single-crystalline Bi2X3 thin films with atomically smooth surface and extremely low-defect density. In particular, we will explore the unique van der Waals epitaxy growth mechanism, providing detailed discussions on the choice of key growth procedures and parameters during the MBE growth. Furthermore, we will introduce advanced growth techniques such as functional doping and structural engineering so that the functionalities can be further multiplied. Finally, we will give an outlook on Bi2X3-based materials system for exploring new physics and device applications.