The thermal effect of rocks not only depends on the temperature level but also may be influenced by the factors including heating environment, heating rate, and cooling method. In this study, approximate vacuum (V) and air circulation (A) heating condition are, respectively, applied on the limestone specimens in the whole heating process. Then, physical, mechanical, and nuclear magnetic resonance (NMR) tests were carried out to investigate the effect of heating conditions on the rock properties. The results show that heating conditions have significant effects on mechanical properties of limestone specimens (including peak strength, elasticity modulus, secant modulus, and crack initiation stress), which are due to the interference effect on the oxidation and thermal decomposition. It is worth noting that the significant temperature range of the heating condition is 450 ∼ 750°C, during which the mechanical performances of heat-treated specimens under V condition obviously outperform those under A condition. Combining the NMR results and the microstructure images from scanning electron microscope (SEM) technology, the evolution of pore distribution was revealed. As temperature increases from room temperature to 900°C, porosity increases gradually. However, pore distribution changes from small and medium pores dominating to large pore dominating and then to medium pore dominating. For limestone specimens after high-temperature treatment above 450°C, mineral crystals may melt and reconsolidate, filling in some of the previously large pores generated by thermal decomposition.