From a rapid combustion and catalyst‐free method, puresingle‐crystalline nanotetrapod‐assembled bulk nano‐ZnO was grown on a gram‐scale for the first time. The gram‐scale bulk nano‐ZnO is synthesized from ZnO powder with great reliability and repeatability, and also a high conversion efficiency. All four arms of the nanotetrapods are cone shaped and grow in the [001] direction. The photoluminescence properties of the nanotetrapod‐assembled ZnO were studied and a mechanism was suggested for the growth of the bulk nanotetrapod‐assembled ZnO. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)