Polystyrene (PS) spheres can self-assemble into colloidal crystal monolayers that are currently employed for template-assisted synthesis of one-dimensional (nanopillars, nanorods, nanowires and nanotubes) nanostructure arrays. Compared to other classes of templates, PS-sphere monolayers can be easily formed and adjusted on substrates, and further manipulated using subsequent growth methods. Recently, several synthetic techniques have been developed and resulted in increased number of publications. Many applications including field-emitters, antireflection, light-emitting diodes (LEDs), photonic crystals, surface wetting, and photocatalysis have been reported utilizing these PS-sphere mediated nanoarrays. In this feature article, these synthetic strategies are highlighted along with a review of the applications emerging from current PS-sphere assisted nanoarrays and future challenges are analyzed.