In the present work, ZnO nanostructures were synthesized by monoethanolamine (MEA)-assisted ultrasonic method at low temperature. Structural analysis was carried out by X-ray diffraction (XRD) confirmed the formation of hexagonal wurtzite structure of ZnO. The effect of ammonia water on the molecular structure of MEA, and its effect on the morphology of ZnO nanostructures were monitored by electron microscopy. Scanning electron microscopy (SEM) results suggest that ZnO nanoparticles with 100 nm in diameter were produced in case of MEA-assisted ultrasonic method. However, as ammonia water was added into the reaction system the morphology of ZnO nanoparticles changed into nanorods, flower-like nanostructures and finally microrods. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies showed that as prepared ZnO nanostructures were single crystalline in nature and grew in different directions resulted in the formation of various structures. The growth mechanism of as prepared ZnO nanostructures was discussed in detail. It was proposed that the addition of ammonia water into the reaction system resulted into the formation of ethylene diamine (EDA) which directed the growth of ZnO. The optical property was studied by photoluminescence (PL) spectroscopy showed only UV emission and no defects mediated visible emission.