We report the preparation of different surface patterns based on the photo-cross-linking/degradation kinetics of polystyrene (PS) by using UV light. Upon exposure to UV light, PS can be initially cross-linked, whereas an excess of the exposure time or intensity provokes the degradation of the material. Typically photolithography employs either positive or negative photoresist layers that upon removal of either the exposed or the nonexposed areas transfer the pattern of the mask. Herein, we present a system that can be both negative and positive depending on several aspects, including the irradiation time, intensity, or presence of absorbing active species (photoinitiators) using a general setup. As a result of the optimization of the time of exposure and the use of an appropriate cover or the incorporation of an appropriate amount of photoinitiator (in this particular case IRG 651), different tailor-made surface patterns can be obtained. Moreover, changes of the chemical composition of the polystyrene using, for instance, block copolymers can lead to surface patterns with variable functional groups. In this study we describe the formation of surface patterns using polystyrene-block-poly(2,3,4,5,6-pentafluorostyrene) block copolymers. The introduction of fluorinated moieties clearly modifies the wettability of the films when compared with that of the same structures obtained with PS. As a consequence we present herein a patterning methodology that can simultaneously vary not only the morphology but also the surface chemical composition.