Owing to the rise in global population and living standards, waste treatment has inevitably become a critical issue for a sustainable environment. In particular, for an effective recycling process, it is vital to disassemble different types of materials by removing adhesives used in the packaging. However, this removal process requires harsh solvents (acidic and organic) that are unfriendly to nature and may cause additional pollution. To address this issue, functional adhesive materials that can be removed without the use of harsh solvents have drawn significant attention. One promising approach is to utilize the stimuli-responsive polymers to synthesize pressure sensitive adhesives (PSAs); however, it is technically challenging to simultaneously satisfy (i) strong initial adhesion (without stimulus), (ii) stimuli-responsive sufficient reduction of adhesion, and (iii) reversibility. In this study, thermo-switchable PSAs were synthesized by copolymerizing N-isopropylacrylamide (NIPAM), which possesses thermal-responsive properties; acrylic acid, which endows adhesive properties; and 2-ethylhexyl acrylate, which has a low glass transition temperature to attain sufficient flexibility. The synthesized NIPAM-based thermo-switchable PSAs exhibited significantly high peel strength at room temperature (∼15.41 N/25 mm at 20 °C), which decreased by ∼97% upon heating (∼0.46 N/25 mm at 80 °C). Importantly, no residues remained due to the cohesive nature of NIPAM at high temperature. The reversible adhesion behaviour of the thermo-switchable PSAs was retained during repeated heating and cooling cycles. Therefore, the developed thermo-switchable PSA can enhance the reusability and recyclability of valuable materials and minimize the use of toxic chemicals for adhesive removal, contributing to a more sustainable future.