Porous structure design and reversible regulation of pore size during adsorption-desorption are crucial to the removal of pollutants in water such as Cr(VI). In this paper, micropores and switchable mesopores were constructed on MCM-41 to further improve adsorption-desorption performance of Cr(VI) via the confinement effect of micropores and opening and closing of mesopores. 2-Vinylpyridine was introduced and polymerized into the pores and on the pore mouth of MCM41 modified by C═C group (AM41) under the irradiation of ultraviolet light. The obtained samples (PM41) possessed mesopores (2.73 nm) and micropores (1.36 nm), where mesopores could open or close under different pH and micropores showed the confinement effect because their pore size is close to Cr(VI) diameter (0.87 nm). Compared with MCM-41, the introduction of poly(2-vinylpyridine) enhanced obviously its adsorptive ability and it trapped most of the Cr(VI) (99%) in solution, 12 times higher than that of the parent sample. The change of pore size is favorable to the cycle performance, and after 3 times recycling, the removal rate of Cr(VI) by PM41-20 remained above 88%. Langmuir isotherm showed a better data correlation than the Freundlich model. Cr(VI) in solution was removed by electrostatic interaction between the pyridine group and Cr(VI) and the confinement effect from micropores.