Phase-change materials (PCMs) are considered one of the promising substances to be engaged passively for thermal management systems through storing and releasing thermal energy in the form of latent heat within melting and solidification processes. However, the existing PCMs pose very low thermal conductivity, leading to an undesirable increase in total thermal resistance and slow thermal response time. This often becomes the bottleneck of the systems from the thermal performance perspective. To address this issue, two types of microencapsulated PCMs are developed depending on the chemical process undergone, both with an average capsule size of 10 to 30 µm whereas the boron nitride (BN) shell thickness is estimated at around 100 nm. While the first type was subject to undergoing a chemical process under vacuum conditions, the second type was produced under non-vacuum conditions. The present study aims to numerically and experimentally investigate the thermal characteristics of both microencapsulated PCMs, and then compare them with the base conventional PCM used to develop the core of microcapsules. Thermal characterization is executed for measuring the melting temperature, latent heat of fusion, and specific heat capacity using the Differential Scanning Calorimetry (DSC) technique as well as for measuring the thermal diffusivity over a range of operating temperatures using the laser flash technique. Material characterization is also conducted for either of the samples using SEM to identify the size and geometry of microcapsules, thickness of capsule shells, and elemental compositions. Furthermore, a numerical simulation will be developed to estimate thermal conductivity of the introduced NE-PCM for comparison and verification purposes with empirical measurements.