An efficient solid-phase based synthesis was presented to covalently bind a large number of molecules with high nonlinear optical (NLO) performance to the surface of colloidal crystalline arrays (CCA) nanoparticles. The nanospheres maintained a large surface charge density due to unaltered sulfate groups. The latexes are chosen with similar electrophoretic characteristics and excellent colloidal stability. The polystyrene spheres are shown to be organized in a periodic lattice or CCA. The nanocrystals formed are shown to be highly stable and the nonlinear conversion is 3 × 104 times larger. The chemically modified crystals provide high coverage of the nanosphere surface and result in more thermally stable resultant systems.