In this manuscript, we demonstrate the control of film thickness and surface wettability in the photochemical immobilization of poly (vinyl alcohol) (PVA) to a self‐assembled monolayer (SAM) containing a phthalimide chromophore. Surface attachment is characterized by ellipsometry and contact angle measurements. The wettability of the resulting films is shown to depend on the chemical composition of the polymer. The film thickness is shown to depend on the irradiation time and molecular weight of the polymer. Using a photomask, micropatterns of polymers can be grafted to the SAM. The photopatterned surface can be “developed” by coating with a thin layer of a mixture containing poly (styrene) (PS) and triphenylsulfonium triflate.