Colloidosomes constructed by the self-assembly of nanoparticles (NPs) on liquid-liquid interfaces have been demonstrated to be useful in many fields. However, the interspaces between NPs on the surface of colloidosomes barricade their application in small molecule encapsulation. Herein, fabrication of a new type of colloidosome built by the seamless connection of NPs via simply heating and quenching a type of core-shell structured NPs (CSNPs) aqueous system using oil as a template, is presented. These colloidosomes have a hollow structure and exhibit efficient small molecule encapsulation. More importantly, the colloidosomes can dissociate into single NPs and release the small target molecules encapsulated in interior of the colloidosomes at a temperature higher than the melting point of the CSNP shell. It is also shown that the dissociation temperature of colloidosomes can be controlled by simply adjusting the length of the PEG chains in the CSNP shell, which implies that these intelligent capsules have attractive application prospects in controlled drug release.National Natural Science Foundation of China[50873082, 30700020]; Research Fund for the Doctoral Program of Higher Education[20070384047]; Scientific and Technical Project of Fujian Province of China[2009J1009, 2010H6021, 2010J01306