Functional assemblies of materials can be realized by tuning the work function and band gap of existing materials. Here we demonstrate the structural assembly of two- and three-dimensional (2-D) and (3-D) nanomaterials and investigate the optical and electronic properties of an assembly of monolayer on a rough polycrystalline NiO surface. Monolayer (2-D material) was transferred onto the NiO surface using a polymer-assisted transfer technique and resulted in a surface roughness about greater than that of on . Raman maps of transferred onto NiO display a spatial nonuniformity of the () and () peak intensities, indicating that regions of the exist in a strained condition on the 3-D NiO surface. Kelvin probe force microscopy measurements show that the assembly has a surface potential lower than that of , whereas that of is higher than NiO, indicating that a monolayer of is sufficient to modify the surface potential by acting as either an electron donor or acceptor with the underlying surface. Thus, 2-D and 3-D materials can be organized into functional assemblies with electron flow controlled by the either as the electron donor or acceptor.