This research investigates the transition from a micropinned to a polymeric alloy structure in crosslinked‐polyethylene‐polystyrene (XLPE‐PS). Incorporating 2 wt% 10 μm PS particles into low‐density polyethylene (LDPE) and crosslinking with 2 wt% dicumyl peroxide (DCP) forms XLPE‐PS structures. The polymeric alloy structure, formed at 220°C extrusion, contrasts with the micropinned formed at 150°C. Morphological, thermo‐structural, chemical, and crystal properties are examined to understand their impact on electrical properties and charge transport mechanisms. Results indicate that the polymeric alloy effectively resolves void/crack issues, whereas the micropinned exhibits phase separation. Both structures exhibit a benzene‐crosslinked network, and variations in these structures lead to significant changes in thermo‐structural, chemical, and crystalline properties. The polymeric alloy XLPE‐PS shifts the polyethylene (PE) hkl crystal planes, confirming phase shift and optimal alloying. The structural alterations reveal deeper traps and higher densities in the polymeric alloy XLPE‐PS, leading to significantly improved electrical properties, including reduced DC conductivity by up to 1.3 and 0.7 decades at 30 and 90°C, and increased DC breakdown strength by up to 40.34% and 16.17% at 30 and 90°C, respectively, compared with micropinned XLPE‐PS. This research offers insights into stable high‐voltage insulation development.