In the present study, the mechanical properties and the residual stress–strain behavior of lightweight concrete (LWC) containing pumice coarse aggregate and rock wool waste (consisting of mineral fibers) were explored prior to and following thermal loading. Key variables included the volume percentage of rock wool waste (0%, 2.5%, 5%, 7.5%, and 10%) and exposure temperature (20°C, 200°C, 400°C, and 600°C). Here, parameters playing a role in the compressive performance of LWC containing rock wool waste were examined. These parameters included the elastic modulus, compressive strength, strain at peak stress, ultimate strain, toughness index, stress–strain relationship, and failure mode. Then, several empirical relationships were proposed to predict different mechanical characteristics in terms of temperature and volume percentage of rock wool. Furthermore, the compressive strength, elastic modulus, and strain at peak stress values were compared to the prediction results of the ACI 216, EN 1994-1-2, ASCE, and CEB-FIP 1990 codes. The results demonstrated that the mechanical properties of the LWC specimens were degraded with temperature. The highest degradation in the temperature range under study occurred at 600°C, with around 50% and 80% drop in the compressive strength and elastic modulus, respectively. Furthermore, after exposure to 600°C, an increase of 2 to 2.8 folds occurred in the strain at peak stress and an increase of 2.6 to 3.4 folds occurred in the ultimate strain of the specimens relative to those at the ambient temperature. In the end, two stress–strain models were presented to capture the compressive performance of LWC including rock wool waste after elevated temperature exposure based on the empirical equations obtained for the mechanical characteristics. These models showed a relatively good correlation with the experimental data.