Block copolymers have been recognized as versatile materials to prepare nanoporous polymer films or membranes, but their potential has not been completely explored. This study focuses on the formation and characterization of nanoporous polymer films based on poly(styrene)-block-(methylmethacrylate/methacrylic acid); (PS-b-MMA/MAA) were obtained through atom transfer radical polymerization (ATRP), by using two different protocols: annealing and annealingirradiation; for improving the formation of microporous surface. The composition, crystallinity and structural order of the films were studied by Raman spectroscopy. The film polymer thickness was obtained through very high resolution ellipsometry (VHRE). Finally, atomic force microcopy (AFM) and scanning electron microscopy (SEM) techniques were used to detect changes in the porous-structure. These results show that the morphological properties of the block copolymer were affected via the modification of two variables, UV-radiation time and annealing. SEM and AFM micrographs showed that the morphology exhibit a porous ordered structure. Contact angle measurement suggests additional interactions between hydrophilic functional groups that influence the film wettability.