Aggregation based meso-scale self-assembly of doped semiconductor nanocrystals leading to the formation of monocrystalline nanorods showing enhanced photo- and electro-luminescence properties is reported. ∼4 nm sized, polycrystalline ZnS nanoparticles of zinc-blende (cubic) structure, doped with Cu+-Al3+ have been aggregated in the aqueous solution and grown into nanorods of length ∼400 nm and aspect ratio ∼12. Transmission electron microscopic (TEM) images indicate crystal growth mechanisms involving particle-to-particle oriented-attachment assisted by sulphur-sulphur catenation leading to covalent-linkage. The nanorods exhibit self-assembly dependant luminescence properties such as quenching of the lattice defect-related emissions accompanied by the enhancement in the dopant-related emission, efficient low-voltage electroluminescence (EL) and super-linear voltage-brightness EL characteristics. This study demonstrates the technological importance of aggregation based self-assembly in doped semiconductor nanosystems. © 2005 Elsevier Ltd. All rights reserved.