In this study, the effects of phase change material (PCM) on the thermo-mechanical behaviors of concrete pavement slabs are investigated so as to test the feasibility of utilizing PCM for mitigation of thermal curling of pavement. The PCM is elaborately stabilized in porous lightweight aggregate then loaded into concrete, without compromising strength associated with PCM incorporation. Thermal analysis indicates that the PCM introduces a latent heat capacity of about 21 J/g to the pavement slab. Two emerging fiber-optic monitoring techniques, i.e., truly distributed strain/temperature sensors and a high-resolution inclinometer, are employed to continuously monitor distributions of the temperature, strain, and tilting angle of the slabs subjected to heating and cooling, respectively. Validated by the obtained experimental results, a finite element simulation framework is established to further investigate the temperature gradient distributions, slab deformations/curvatures, and thermal strain and stress inside the slabs. The results suggest that the PCM-incorporated slab has a higher top surface temperature, a larger top-vs-bottom surface temperature difference, and thereof a larger curvature. However, the temeprature gradient reveals that heat accumulates at the upper layer before PCM melts completely, thus accounting for most of the temerpature difference. Moreover, regardless of the larger top-vs-bottom strain difference and stress nonlinearity, the linear strain of the PCM slab is smaller due to its lower coefficient of thermal expansion, and the later stage stress at the middle of the PCM slab center is smaller. Based on the findings, strategies of using PCM to control thermal curling of pavement slabs are proposed.