A new crosslinking system based on azide-functionalized random copolymers has been defined for the preparation of substrates with controllable surface interactions. The azido group is used for both thermal- and photo-crosslinking, which is found to be very efficient. Furthermore, the use of UV irradiation for crosslinking enables the preparation of patterned surfaces by conventional photolithographic techniques, combining the "bottom-up" self-assembly of block copolymer strategies with traditional "top-down" photolithographic methods.