In CsW2O6, which undergoes a metal-insulator transition (MIT) at 213 K, the emergence of exotic properties associated with rattling motion of Cs is expected owing to its characteristic β-pyrochlore-type structure. However, a hurdle for crystal growth hampers elucidation of detailed properties and mechanisms of the MIT. Here we report on the epitaxial growth of β-pyrochlore-type CsW2O6 films and their electronic properties across the MIT. Using pulsed-laser deposition technique, we grew single-crystalline CsW2O6 films exhibiting remarkably lower resistivity compared with a polycrystalline bulk and sharp MIT around 200 K. Negative magnetoresistance and a positive Hall coefficient were found, which became pronounced below 200 K. The valence-band and core-level photoemission spectra indicated the drastic changes across the MIT. In the valence-band photoemission spectrum, the finite density of states was observed at the Fermi level in the metallic phase. In contrast, an energy gap appeared in the insulating phase. The split of W4f core-level spectrum suggested the charge disproportionation of W5+ and W6+ in the insulating phase. The change of spectral shape in the Cs4d core levels reflected the rattling motion of Cs+ cations. These results strongly suggest that CsW2O6 is an exotic material in which MIT is driven by the charge disproportionation associated with the rattling motion.