The tunable surface-wetting properties of photosensitive random copolymer mats were used to spatially control the orientations of thin-film block copolymer (BCP) structures. A photosensitive mat was produced via thermal treatment on spin-coated random copolymers of poly(styrene-ran-2-nitrobenzyl methacrylate-ran-glycidyl methacrylate), synthesized via reversible-deactivation radical polymerization. The degree of UV-induced deprotection of the nitrobenzyl esters in the mat was precisely controlled through the amount of UV-irradiation energy imparted to the mat. The resulting polarity switching of the constituents collectively altered the interfacial wetting properties of the mat, and the tunability allowed lamellar or cylinder-forming poly(styrene-b-methyl methacrylate) BCP thin films, applied over the mat, to change the domain orientation from perpendicular to parallel at proper UV exposures. UV irradiation passing through a photomask was capable of generating defined regions of BCP domains with targeted orientations.