Molecular imprinting, an important methodology for the straightforward prepared of antibody-like polymers, is recently one of focuses in chemistry because of its importance in catalysis, separation and sensing. Described usually as a ‘from-key-to-lock’ process, the molecular imprinting recognizes and interacts with substrates basing on a specifically complementary framework. The present proposal aims to design ‘smart’ imprinted polymers capable of showing tunable catalysis. Inspired by recent advances in the ‘Smart’ technology, a unique hydrophilic/hydrophobic transition is created within the binding framework. The design of this transition will cause an opening/closing-tunable mechanism within the binding framework, thereby allowing/refusing the substrates in water accessible to the interior. In the opening state, the substrate in water can be freely accessible to the binding framework, thus making possible efficient interaction. Above the transition the blockage of access to the inner largely restricts the diffusion of substrates. In this way, such recognition and catalysis are comparable to an on/off-switchable process, which thus allows one to manipulate the activity by controlling the phase behaviours of prepared materials.