Binary thermosensitive nanocomposites are fabricated by grafting block copolymers of poly(N-isopropylacrylamide) and poly(methoxy-oligo (ethylene glycol) methacrylate) onto gold nanoparticles through consecutive, surface-initiated, atom-transfer radical polymerization (ATRP). These Au@copolymer nanocomposites display a well-defined core/shell nanostructure and have two thermosensitive points near 33 and 55 degrees C in an aqueous suspension corresponding to the thermally induced conformational transition of inner homopolymer segments and outer oligo(ethylene glycol)-containing copolymer layer, respectively. Silver nanoparticles trapped within Au@copolymer nanocomposites with weakly crosslinked shells display thermally modulated catalytic activity as heterogeneous catalysts because of the thermosensitive collapse of the polymer layers.