We present results from an experimental study of ordering characteristics in monolayers of polystyrene nanospheres self-assembled at a water-air interface. We demonstrate that the interaction of spheres, governed by the dissemination of surface charge, leads to the formation of macroscopic close-packed ordered areas or "domains" with a well-defined orientation of the lattice axes over areas of 25 mm(2). It was found that by changing the surface chemistry of the spheres it is possible to modify the balance between the attractive and repulsive forces and thus to control the ordering characteristics. We implemented a model that simulates the process of self-assembly and examines the ordering characteristics for layers with different ratio between attractive and repulsive forces. A good qualitative agreement was found between the simulations and experiment. These studies are technologically relevant as a method of producing nanosphere templates for large area patterned materials.