A simple method to prepare large areas of polycarbonate (PC) alignment layers with a high degree of polymer chain orientation, a periodic and oriented nanoscale pattern, and a controlled surface roughness is presented. The method involves three steps: (i) the preparation of a film of bisphenol A polycarbonate in its glassy state, (ii) the near-surface orientation of the polymer chains by rubbing, and (iii) exposure to vapors of acetone which acts as a plasticizer removing the microgrooves formed by rubbing and promotes solvent induced crystallization of PC. The resulting surface of the PC films is oriented and nanostructured, it consists of the periodic alternation of edge-on oriented crystalline lamellae and amorphous interlamellar zones with a total periodicity of ∼20 nm. The roughness of the oriented and nanostructured PC layers can be tuned by adjusting the exposure time to the solvent. The PC films exhibit a high orienting ability for various materials grown from the vapor phase, e.g., conjugated organic semiconductors and dyes (pentacene, phthalocyanine, bisazo dye) and metallic nanoparticles. Zinc phthalocyanine nanocrystallites and gold nanoparticles are observed to orient parallel to the crystalline lamellae of the PC substrate and not, as observed for polyimides, parallel to the polymer chain direction. It is proposed that the shallow surface nanocorrugation associated with the semicrystalline structure of the PC layers enforces the orientation of the ZnPc nanocrystallites and the gold nanoparticles.