The aim of this study was to enhance the thermal comfort properties of crude glycerol (CG) derived polyurethane foams (PUFs) using phase change materials (PCMs) (2.5–10.0% (wt/wt)) to contribute to the reduction of the use of non-renewable resources and increase energy savings. The main challenge when adding PCM to PUFs is to combine the low conductivity of PUFs whilst taking advantage of the heat released/absorbed by PCMs to achieve efficient thermal regulation. The solution considered to overcome this limitation was to use expandable graphite (EG) (0.50–1.50% (wt/wt)). The results obtained show that the use of PCMs increased the heterogeneity of the foams cellular structure and that the incorporation of PCMs and EG increased the stiffness of the ensuing composite PUFs acting as filler-reinforcing materials. However, these fillers also caused a substantial increase of the thermal conductivity and density of the ensuing foams which limited their thermal energy storage. Therefore, numerical simulations were carried using a single layer panel and the thermal and physical properties measured to evaluate the behavior of a composite PUF panel with different compositions, and guide future formulations to attain more effective results in respect to temperature buffering and temperature peak delay.