Bi2Se3 possesses a two-dimensional layered rhombohedral crystal structure, where the quintuple layers (QLs) are covalently bonded within the layers but weakly held together by van der Waals forces between the adjacent QLs. It is also pointed out that Bi2Se3 is a topological insulator, making it a promising candidate for a wide range of electronic and optoelectronic applications. In this study, we investigate the growth of high-quality Bi2Se3 thin films on mica by the molecular beam epitaxy technique. The films exhibited a layered structure and highly c-axis-preferred growth orientation with an XRD rocking curve full-width at half-maximum (FWHM) of 0.088°, clearly demonstrating excellent crystallinity for the Bi2Se3 deposited on the mica substrate. The growth mechanism was studied by using an interface model associated with the coincidence site lattice unit (CSLU) developed for van der Waals epitaxies. This high (001) texture favors electron transport in the material. Hall measurements revealed a mobility of 726 cm2/(Vs) at room temperature and up to 1469 cm2/(Vs) at 12 K. The results illustrate excellent electron mobility arising from the superior crystallinity of the films with significant implications for applications in conducting electrodes in optoelectronic devices on flexible substrates.