Light reflection from computer monitors, car dashboards and any other optical surface can impair the legibility of displays, degrade transmission of optical components and in some cases may even pose safety hazards. Antireflective coatings are therefore widely used, but existing antireflection technologies often perform sub-optimally or are expensive to implement. Here we present an alternative approach to antireflection coatings, based on an extension of our photo-aligning and photo-patterning technology for liquid-crystal displays (LCDs) and liquid-crystal polymer films with smooth surfaces to optical polymer films with controlled surface topologies. Nano- and micro-corrugated topologies are shown to result from optically induced monomer phase-separation on the polymer surfaces. The properties of the resulting films make them suitable high-performance and low-cost antireflection coatings for optical components of virtually any size, shape and material. Moreover, the approach can be used to form a wide range of other functional polymer thin films with isotropic as well as anisotropic topologies. For example, films can be produced whose optical birefringence exceeds that of the birefringence of the polymer material itself. These new films can also be used as diffractive thin films, diffusers, and directional reflectors which preserve light polarization, or as substrates for aligning liquid crystals to produce bright, low-power-consumption LCDs with integrated optical functions and memory.