In this paper, we present a novel method to generate ultra-small droplets via volatile component evaporation. By regulating the composition of the binary solvent, the volume ratio of the high saturated vapor pressure component, and the flow rate ratio of the two phases, monodisperse ultra-small water or nonvolatile organic droplets can be formed. This method is flexible, versatile, and compatible with tip-streaming or nanofluidics, and may have potential applications in single molecule assay, colloid synthesis, and block copolymer assembly.