Heat-assisted development of shale oil and gas is recognized as a vital technique for the efficient extraction of shale gas; however, there is a need for comprehensive investigation regarding radon release during the extraction process. The aim of this study was to investigate the pore structure and radon release characteristics of heat-treated black shale using low-temperature nitrogen adsorption (LTNA) and radon (Rn-222) measurement equipment. The findings reveal that temperature initially enhances radon release, which subsequently decreases. The maximum radon release occurs at 500 °C, reaching 1.46 times the initial stage. The radon release rate is positively correlated with the volume of micropores (< 2 nm) in the shale. Organic pores within the shale serve as the primary storage spaces for radon, and the intricate pore structure of organic matter provides an optimal environment for radon gas retention. These results contribute to elucidating the mechanisms behind the impact of thermal treatment on shale's radon release rate, which is crucial for guiding radon radiation evaluation in thermal treatment processes.