Herein we present a new perspective showing that water-soluble liquids,when added to water,undergo transient emulsification before complete dissolution.Thus,non-amphiphilic macromolecules can self-assemble at the two-miscible-phase interface when cononsolvent effect appears.A representative case shown here is that when poly(N-isopropylacrylamide)(PNIPAm),prepared by aqueous radical polymerization,in methanol solution is added into water,the polymer chains rapidly self-assemble into hollow micro-vesicles based on the cononsolvency at water/methanol interface.This finding provides a subtle strategy to prepare hollow micro-vesicles by non-amphiphilic polymers without template participating.We proposed a new concept"interfacial cononsolvency"to describe the formation process.Due to the easy modification process,sugar-contained PNIPAm chains are synthesized by copolymerization.As an application example,it is shown that these sugar-contained PNIPAm chains can afford"sweet"micro-vesicles(containing glucose residues).And the"sweet"micro-vesicles can well mimick the protocells which are involved in the recognition of bacteria.