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ZnO: Ag (0–20 mol%) hexagonal nanostructures were prepared via the phyto-synthesis route using Chonemorpha fragrans leaf extract. The structure, morphology, and compositions of the as-formed product were characterized by powder X-ray diffraction (PXRD), Field Emission Scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Surface-enhanced area diffraction (SEAD), and Raman spectroscopy. Further, prepared nanostructures were subjected to sensor and luminescence studies. PXRD pattern shows the formation of the hexagonal wurtzite system. The Rietveld refinement analysis is used to refine structural parameters. FESEM micrographs show the agglomeration of the nanoparticles. The TEM pictures reveal the hexagonal shaped nanoparticles. The average 30 - 35 nm ranged crystallite sizes were determined using Scherrer's method which is in good agreement with the TEM. An economical and naturally responsive strategy can be the use of plant extract in the synthesis of nanostructured products. Also, studies related to sensing of paracetamol were performed using ZnO: Ag (20 mol%) indicating that it is a promising electrode material for paracetamol sensing. The identified PL emission bands indicate favorable luminescence applications for ZnO: Ag nanopowders.