The current challenge for polymeric nano reactors is to precisely control the membrane permeability between permeable, impermeable, and semipermeable at defined pH. Additionally, the synthetic methods are obstructed by tedious purification processes, especially when polymer multiblocks are required in the membrane of capsules to achieve different responsiveness and functions. Here, we report a rapid one-pot synthesis of ABA-type triblock copolymer brushes on silica template via surface-initiated single electron transfer living radical polymerization (SI-SET-LRP). It is worth noting that there is no purification between the successive block formation steps, since each step is taken to full translation within 20 min. After removing the template, hollow capsules with cross-linked membrane are obtained and have been used as multiresponsive nanoreactors for enzymatic reactions. Their membrane permeability is triggered primarily by temperature and secondarily by pH to allow controlled enzymatic reactions to be reversibly addressable between "permeable", "semipermeable", and "impermeable" valve-like membrane status. These valve-like features highlight the significant potential of hollow capsules, for example, in the fields of synthetic biology and enzyme-deficient disease therapeutic applications.