Fluorescent nanodroplets of liquid crystal (LC) were generated by the electrospray deposition of LC solvent containing rhodamine 6G (Rh6G) dye molecules. The shape and density of the nanodroplets strongly depended on the concentration of LC diluted with ethanol solution. The fluorescent spectra from the Rh6G molecules in LC nanodroplets were obviously blue-shifted compared with the LC films of the bulk state. Furthermore, the LC nanodroplets were dispersed on a metallic nanograting formed by optically modifying an azobenzene thin-film layer under the metallic film. The nanodroplets were size-selectively aligned on the metallic nanograting.