Ferroelectric domain patterns are used as templates on which rare earth doped high refractive index nanoparticles activated with trivalent rare earth ions (RE(3+)) are selectively assembled on domain surfaces with a specific polarization. Two-dimensional luminescent heterostructures, with sizes and geometries defined by the ferroelectric patterning are achieved. The process of incorporation and consolidation of the optically active nanoparticles into the alternate domain structures leads to luminescent ring-shaped arrangements with innovative geometries and to a micrometer spatial control of the trivalent rare earth ion emitters. Multicolor emission systems and the possibility of chromatic switching at the micrometer scale among the three different compounds forming the two dimensional structure is demonstrated.