A new AuNPs-based thermosensitive nanoreactor (SiO₂@PMBA@Au@PNIPAM) was designed and prepared by stabilizing AuNPs in the layer of poly(N,N’-methylenebisacrylamide) (PMBA) and subsequent wrapping with the temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) layer. The new nanoreactor exhibited high dispersibility and stability in aqueous solution and effectively prevented the aggregation of AuNPs caused by the phase transformation of PNIPAM. The XPS and ATR-FTIR results indicated that AuNPs could be well stabilized by PMBA due to the electron transfer between the N atoms of amide groups in the PMBA and Au atoms of AuNPs. The catalytic activity and thermoresponsive property of the new nanoreactor were invested by the reduction of the environmental pollutant, 4-nitrophenol (4-NP), with NaBH₄ as a reductant. It exhibited a higher catalytic activity at 20 °C and 30 °C (below LCST of PNIPAM), but an inhibited catalytic activity at 40 °C (above LCST of PNIPAM). The PNIPAM layer played a switching role in controlling the catalytic rate by altering the reaction temperature. In addition, this nanoreactor showed an easily recyclable property due to the existence of a silica core and also preserved a rather high catalytic efficiency after 16 times of recycling.