As a result of human underground mining activities, phyllite has been extensively reused to make raw ceramic materials and concrete aggregates. Building materials are a significant source of indoor radon, and radon gas emitted from phyllite poses radiation risks to humans. High temperatures can alter the structural properties of rocks, impacting radon exhalation. Thus, this study examined phyllite's radon exhalation rate after heat treatment ranging from 25 °C to 1000 °C. The effects of changes in pore structure and mineral composition on phyllite's radon exhalation were analyzed in detail using nuclear magnetic resonance (NMR), polarizing optical microscopy (POM), three-dimensional microscopy (3DM), and scanning electron microscopy (SEM). Results indicate that the radon exhalation rate initially increases and then decreases with rising temperature. This rate correlates positively with both total porosity and micropore porosity. Processes such as free water evaporation, pyrite oxidation, quartz phase transformation, and chlorite dehydroxylation within phyllite contribute to pore development and the movement of free radon within pore spaces. The highest total porosity and radon exhalation rate occur at 700 °C, measuring 8.6 % and 6.14 Bq/m2·h, respectively—4.30 times and 1.18 times higher than at 25 °C. Additionally, mineral decomposition and melting reduce pore connectivity and effective porosity, hindering radon migration. These findings offer guidance for assessing radon radiation risks and indoor radon potential in phyllite-based building materials.