Gradient copolymer grafts of styrene and α-tert-butoxy-ω-vinylbenzyl-poly(glycidol ethoxyethyl ether) (PGLet), a precursor of α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (PGL), were prepared on silicon wafers via a surface-initiated activator generated by electron transfer radical polymerization (AGET ATRP). Silicon plates with previously attached 2-bromoisobutyrate served as a macroinitiator for the AGET ATRP (activator generated by electron transfer) of styrene and PGLet. The copolymers' gradient P(S-co-PPGL) of composition and thickness was obtained by a simple method where the plates were slowly removed from reaction mixture using a step motor. PGLet was added continuously (dropwise) into the reactor during withdrawal of the plates from solution in order to increase the relative concentration of PGLet in polymerization mixture. A range of strategies of making grafts was tested. The plates with copolymers grafts were analyzed by various techniques, like XPS, ellipsometry, and FTIR spectroscopy. The results indicate that the AGET ATRP process is dependent on the styrene/PGLet macromonomer ratio in the polymerization mixture. Under optimal conditions, the addition of PGLet during polymerization and subsequent deprotection of hydroxyl groups of PGLet permit to obtain plates with a novel copolymer layer with composition, thickness, and wettability gradient. Plates with chemical composition of copolymer grafts gradient served as versatile supports with controlled hydrophilic/hydrophobic area and were suitable for tailored deposition of particles.