A zipper-like on/off-switchable molecularly imprinted polymer is reported. This unique imprinted polymer was composed of template-imprinted polymeric networks that incorporate zipper-like interactions between poly(acrylamide) (PAAm) and poly(2-acrylamide-2-methyl propanesulfonic acid) (PAMPS). This polymer showed marginal recognition ability towards the imprint species under low temperature conditions, due to the interpolymer interaction between PAAm and PAMPS, which inhibited access to the imprinted networks. In contrast, at relatively high temperatures (such as 40 °C), the polymer demonstrated significant molecular recognition ability towards the imprint species resulting from the dissociation of the interpolymer complexes of PAAm and PAMPS, which enabled access to the imprint networks. Unlike previously reported PNIPAm-based imprinted polymers, which demonstrate alterable molecular recognition simply because of the thermosensitive hydrophilicity/hydrophobicity of PNIPAm, this polymer employed a zipper-like supramolecular architecture between PAAm and PAMPS, thereby enabling switchable molecular recognition.