Ordered self-assembled nanopatterns have attracted much attention for their ability to mimic moth-eye structures and display unique optical properties. In the study, emulsifier-free emulsion polymerization was performed to prepare polystyrene nanospheres with uniform size distribution. Various hydrophilic monomers were added to copolymerize with styrene, including 2-hydroxyethyl methacrylate, acrylic acid, and methyl acrylic acid, respectively, to enhance the self-assembling ability of nanospheres. The nanosphere suspension was injected into an air-water interface to self-assemble a nanosphere array, and then the resulting photonic crystal film was deposited on a substrate using a scooping transfer technique. The layer-by-layer scooping transfer technique can be applied to produce 2D and 3D assembled nanosphere layers on an area as large as a 4-inch wafer. The pattern of the 2D nanosphere array was attached to a UV-curable precursor surface and then encapsulated and transferred to the crosslinked resin after UV irradiation. The sample was then immersed into some solvents which could partially swell the resin surface to produce nanoball structures or etch the surface to generate nanobowl structures. The size of the as-prepared polystyrene spheres was about 360 nm, while the feature size of the nanoballs was about 230 nm after undergoing acetonitrile swelling. The facile and inexpensive technique can be applied to produce ordered nanoball patterns for various applications, such as optical coatings, superhydrophobic coatings, biophotosensors, antireflection films, dry adhesives, and so on. (C) 2014 Elsevier B. V. All rights reserved.