In this study, we combined the imprinting technique, temperature‐sensitive polymer, and Pickering emulsion polymerization to prepare a temperature‐sensitive porous imprinted polymer. First, the temperature‐sensitive block polymer PDEA‐b‐P (DEA‐co‐AM) was prepared by reversible‐addition fragmentation chain transfer polymerization, and then a temperature‐sensitive porous ReO4− imprinted polymer (ReO4−‐TPIP) was prepared using the Pickering‐like polymerization technique, which was introduced to the preparation of the imprinted polymer. The structure and morphology of the polymer were characterized by FTIR, SEM‐EDS, and BET. The adsorption experiments showed that the maximum adsorption (Q), separation (R), and desorption (D) of ReO4−‐TPIP were 0.1568 mmol/g, 3.41, and 85.22%, respectively, and the adsorption equilibrium could be reached after 120 min, which decreased to 0.1212 mmol/g, 1.23, and 70.01% after repeated use for 11 times. These results indicate that ReO4−‐TPIP has good adsorption and reusability properties. The adsorption studies showed that ReO4−‐TPIP conformed to the zero‐level kinetic model in the pre‐adsorption stage, the quasi‐one‐level kinetic model in the late stage, and the isothermal adsorption process conformed more to the Langmuir model. In addition, in the secondary leach solution of high‐temperature alloys, the purity of rhenium in the solution increased from 35.4119% to 53.4812% after one adsorption/desorption cycle. The prepared ReO4−‐TPIP provides a new material and strategy for the selective separation and purification of rhenium in complex rhenium‐containing solutions for the industry.