Thermosensitive hydrogels are among the most promising class of catalysts for self-controlled tandem catalytic systems. In this study, we developed a bi-layered, molecularly imprinted, thermosensitive hydrogel catalyst that is loaded with silver metal nanoparticles (Ag NPs) and acidic sites. This catalyst is capable of regulating alternating single and tandem reactions, making it a valuable tool for complicated catalytic applications. The catalyst displays two key phase transition temperatures, at 37 °C and 46 °C, by combining positive and negative response temperature-sensitive hydrogel layers together, enabling crossing range responsive ability of the "open" or "closed" state of the substrate channels. Meanwhile, the hydrogel layers can effectively separate the different catalytic sites to prevent active sites and intermediate products from mixing and causing cross-reactions. The opposite thermosensitive characteristics of the hydrogels coupled together produce a swelling-contraction behavior, enabling efficient sequencing of single/tandem/non-catalytic reactions. Overall, this study presents a promising strategy for the development of smart hydrogel catalysts in self-controlling tandem catalytic systems.