By grafting (aminopropyl)triethoxysilane (APTES) as the buffer layer on poly(ethylene terephthalate) (PET) surface, the SAMs of octadecyltrichlorosilane (OTS), phenyltrichlorosilane (PTCS), vinyltrichlorosilane (VTCS), and p-tolyltrichlorosilane (TTCS) were fabricated on the flexible polymer substrate. The properties of SAMs were accurately controlled by adjusting the immersing time of substrates in the solutions and the concentration of the solutions. The SAMs acted as templates, and TiO2 micropattern was successfully deposited on OTS, TTCS, and PTCS SAMs.