Porous polymers have been used for various applications like catalysis, absorption, drug delivery, tissue engineering, and more on. For these applications, thermal behaviour of a material plays a crucial role affecting the material properties. However, the effect of porosity on the thermal properties of porous polymers has scantly been reported. Addressing this, polymeric constructs with varying levels of porosity were fabricated by utilizing Pickering emulsion templating. Stable emulsions of ε-caprolactone (CL) were prepared using silica nanoparticles (SiNP) as stabilizers and silicone oil as dispersed phase, which were further in-situ polymerized and crosslinked. The extent of porosity was controlled by changing the dispersed phase volume percentage of these emulsions. The crystallization behaviour of the polymer present at the interface between two droplets was investigated under non-isothermal conditions due to its better relevance during real-time application. It was observed that inclusion of SiNP and porosity led to extremely diminished crystallization temperature and kinetics. Various models, namely Jeziorny, Ozawa, and Mo models, were utilized to explain the crystallization behaviour of substrates under non-isothermal conditions. While a 3-regime crystallization was demonstrated by non-crosslinked and crosslinked PCL, presence of SiNP and porosity led to 2-regime crystallization. This change in crystallization kinetics of the material was further prominent in materials with higher extent of porosity. Additionally, the changes in crystal structure of various polymer materials were observed using x-ray diffractometer explaining the crystallization behaviour of the porous constructs.