A self-switchable polymer reactor with a hyperbranched structure for controlled catalytic chemistry processes is reported. This polymer reactor was made of silver nanoparticles and a polymer carrier consisting of hyperbranched polyethylenimine and hydroxyethyl acrylate that behaved as thermally switchable domains. Below the transfer temperature, relatively strong catalytic reactivity was demonstrated due to the leading role of hydrophilic groups in the switchable domains, which opened access to the substrate for the packaged silver nanoparticles. In contrast, it showed weak catalysis at relatively high temperatures, reducing from the significantly increased hydrophobicity in the switchable domains. In this way, the polymer reactor displays controllable, tunable, catalytic activity based on this approach. This novel design opens up the opportunity to develop intelligent polymer reactors for controlled catalytic processes.