The need to increase crop productivity and resistance directs interest in nanotechnology. Indeed, biogenic metal oxide nanoparticles can promote beneficial effects in plants, while their synthesis avoids the environmental impacts of conventional synthetic procedures. In this context, this research aimed to synthesize biogenic zinc oxide nanoparticles (ZnO-NPs) using, for the first time, an extract of a wild and spontaneous aquatic species, Lemna minor (duckweed). The effectiveness of this biogenic synthesis was evidenced for comparison with non-biogenic ZnO-NPs (obtained without using the plant extract), which have been synthesized in this research. XRD (X-ray diffraction), FE-SEM (field emission gun electron scanning microscopy), EDX (energy dispersive x-ray spectroscopy), TEM (transmission electron microscope) and UV-vis (ultraviolet-visible spectrophotometry) showed the biogenic approach effectiveness. The duckweed extract was subjected to UHPLC-ESI/QTOF-MS (ultra high-pressure liquid chromatography quadrupole time of flight mass spectrometry) phenolic profiling. This untargeted characterization highlighted a high and chemically diverse content in the duckweed extract of compounds potentially implicated in nanoparticulation. From an application standpoint, the effect of biogenic nanoparticles was investigated on some traits of maize subjected to seed priming with a wide range of biogenic ZnO-NPs concentrations. Inductive effects on the shoot and root biomass development were ascertained concerning the applied dosage. Furthermore, the biogenic ZnO-NPs stimulated the content of chlorophylls, carotenoids, and anthocyanin. Finally, the study of malondialdehyde content (MDA) as a marker of the oxidative status further highlighted the beneficial and positive action of the biogenic ZnO-NPs on maize.