We investigate the self-assembly of colloidal spheres on periodically patterned templates. The surface potentials and the surface phases are induced entropically by the presence of dissolved, nonadsorbing polymers. A rich variety of two-dimensional fluidlike and solidlike phases was observed to form on template potentials with both one- and two-dimensional symmetry. The same methodology was then used to nucleate an oriented single fcc crystal more than 30 layers thick. The general approach provides a new route for directed self-assembly of novel mesoscopic structures.