[en] Multiwalled carbon nanotubes (MWNTs) have been successfully modified with ZnO nanostructures by zinc-ammonitum complex ion covalently attached to the MWNTs through the C-N bonds. Flower-like ZnO on the tips of MWNTs and ZnO nanoparticles on the surface of MWNTs have been obtained, respectively, via adjusting the reaction time. The modified MWNTs have been characterized with X-ray diffraction, scanning electron and transmission electron microscopy. A growth mechanism has been proposed in which the soaking time plays a key role in controlling the size, morphology, and site of ZnO nanostructures. Photoluminescence properties of the as-synthesized products have also been investigated. - Multiwalled carbon nanotube (MWNT)/flower-like ZnO heterojunctions and MWNT/ZnO nanoparticle composites were prepared by zinc-ammonitum complex ion covalently attached to the MWNTs through the C-N bonds via adjusting the reaction time. A growth mechanism has been proposed in which the soaking time plays a key role in controlling the size, morphology, and site of ZnO nanostructures