ZnO nanostructures were grown on Si (111) substrates using Pulsed Laser Deposition. The impact of growth temperature (Ts) and Ar pressure (P Ar) on the morphology, crystal structure and photoluminescence was investigated. Various types of ZnO nanostructures were obtained. Self-forming arrays of vertically-aligned nanorods and nanocones with strong c-axis crystallographic orientation and good optical response were obtained at higher Ts. The nanocone, or "moth-eye" type structures were selected for LED development because of their graded effective refractive index, which could facilitate improved light extraction at the LED/air interface. Such moth-eye arrays were grown on p-type Si (111) substrates to form heteroj unction LEDs with the n-type ZnO nanocones acting as an active component of the device. These nanostructured LEDs gave rectifying I/V characteristics with a threshold voltage of about 6V and a blueish-white electroluminescence, which was clearly visible to the naked eye.