The heat treatment effect on kaolin waste from mining was evaluated on the structural and thermal behavior of poly(ε-caprolactone) (PCL). The PCL/KW (kaolin waste) and PCL/HTKW (heat-treated kaolin waste) composites were processed in an internal mixer and subsequently characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The kaolin waste showed kaolinite and quartz in its composition, while the heat treatment at 1200°C modified it to mullite, quartz and silica-rich amorphous phase. By XRD, there was an increase in the intensity of the peak 2θ = 23.9° of the PCL/KW composites compared to neat PCL. In contrast, PCL/HTKW composites tended to reduce the intensity of the peak 2θ = 23.9°, especially at 5% HTKW. The crystalline melting temperature and the degree of crystallinity of PCL/KW and PCL/HTKW composites were practically unchanged, compared to PCL. However, the crystallization process was more effective with the kaolin waste (KW) without heat treatment, indicating that the HTKW amorphous phase inhibited crystallization. The PCL/KW development promoted an increase in crystallization temperature, relative crystallinity, and crystallization rate, surpassing PCL and the PCL/HTKW system. In view of this, kaolin waste has the potential to accelerate the PCL crystallization process, contributing to add value to a material that would otherwise be discarded and minimizing environmental impacts.