Langmuir-Blodgett (LB) assembly is a classical molecular thin-film processing technique, in which the material is spread onto water surface from a volatile, water-immiscible solvent to create floating monolayers that can be later transferred to solid substrates. LB has also been applied to prepare colloidal thin films with an unparalleled level of microstructural control and thickness, which has enabled the discovery of many exciting collective properties of nanoparticles and the construction of bulk nanostructured materials. To maximize the benefits of LB assembly, the nanoparticles should be well dispersed in both the spreading solvent and on water. This is quite challenging since colloids usually need contrasting surface properties in order to be stable in the water-hating organic solvents and on water surface. In addition, many organic and polymeric nanostructures dissolve in those organic solvents and cannot be processed directly. Using water-liking spreading solvents can avoid this dilemma. However, spreading of water-miscible solvents on water surface is fundamentally challenging due to extensive mixing, which results in significant material loss. Here we report a conceptually simple strategy and a general technique that allows nearly exclusive spreading of such solvents on water surface using electrospray. Since the volume of these aerosolized droplets is reduced by many orders of magnitude, they are readily depleted during the initial spreading step before any significant mixing could occur. The new strategy drastically reduces the burden of material processing prior to assembly and broadens the scope of LB assembly to previously hard-to-process materials. It also avoids the use of toxic volatile organic spreading solvents, improves the reproducibility, and can be readily automated, making LB assembly a more robust tool for colloidal assembly and thin-film fabrication.