A thermal-sensitive "jelly" was used to control the diffusion of a diamine monomer for synthesizing polyamide free-standing nanofilms with an adjustable thickness of 5-35 nm. The reduced reaction rate of the interfacial polymerization at the hexane-"jelly" interface made the synthesized nanofilms show high water permeation flux and suitable salt rejection, and they also have highly negative surface charges and fairly smooth surfaces.