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How to furnish catalysts with switchable catalytic ability is a challenge in self-controlled catalysis. This issue was addressed by constructing a unique polymer nanoreactor containing 'mobility-recalling' switchable domains that acted as a molecular switch for providing access to the encapsulated metal nanoparticles. This polymer reactor revealed poor reactivity at relatively low temperatures because of the 'frozen' molecular chains in the switchable domains inhibiting the access of substrate to the encapsulated metal nanoparticles (i.e., catalytic 'off' status). In contrast, the polymer reactor demonstrated significant reactivity at relatively high temperatures, resulting from the dramatically increased mobility of the molecular chains, which allowed access to the encapsulated nickel nanoparticles (i.e., catalytic 'on' status). Switching between the catalytic off and on statuses could be repeated owing to the recallable mobility of molecular chains in the switchable domains. This protocol opens up the opportunity to develop smart nanoreactors for controlled chemical processes. [ABSTRACT FROM AUTHOR]