A Polyol method has granted low-cost and facile process-controllability for silver-nanowire (Ag-NW) synthesis. Although homogenous and heterogeneous nucleation and growth during Ag-NW synthesis are possible using polyol methods, heterogeneous nucleation and growth of Ag NW guarantees highly selective growth of nanostructures using silver chloride (AgCl) seeds, which provides a stable source of chloride ions (Cl-) and thermodynamic reversibility. In this paper, a microdroplet has been adopted to synthesize uniform AgCl seeds with different diameter that are used for seed-mediated Ag-NW synthesis. The concentration of two precursors (AgNO3 and NaCl) in the droplets is modulated to produce different sizes of AgCl seeds, which determines the diameter and length of Ag NWs. The process of the seed-mediated growth of Ag NWs has been monitored by observing the peak shift in the time-resolved UV-vis extinction spectrum. Furthermore, the distinct plasmonic property of Ag NWs for transverse and longitudinal localized-surface-plasmon-resonance (LSPR)-mediated fluorescence enhancement is utilized. The high aspect ratio and sharp tips work as simple antennas that induce the enhanced fluorescence emission intensity of a fluorophore, which can be applied in the fields of biological tissue imaging and therapy.