This research work is the first to report thermal stability, heat deformation resistance, and crystallization behavior of a Polyethylene (PE)-based biphasic polyolefin system reinforced with Reduced Graphene Oxide (RGO), which was obtained through Graphene Oxide (GO) chemical reduction. Polypropylene (PP) represented the polymeric dispersed phase. A strategic PE/PP/RGO manufacturing procedure was employed to thermodynamically localize RGO at the PE/PP interface, as confirmed by Transmission Electron Microscopy (TEM), bringing a uniform micro phase dispersion into the macro phase. In addition, studies of PE non-isothermal crystallization kinetics indicated that the morphology tunable micro phase and the nanolayered RGO promoted a nucleation-controlled PE crystallization, which was supported by Polarized Light Optical Microscopy (PLOM). This, together with fine morphology, justified the remarkable enhancement registered for the ternary system’s thermal stability and heat deformation resistance. Different filler loads were employed, with weight fractions of 2% and 4%. It was observed that the former, being better exfoliated and more homogeneously distributed at the PE/PP interface than the latter, led to a more improved PE crystallization, alongside a greater ternary system’s thermal properties. Moreover, the thermal stability of PE/PP reinforced with 2% of RGO was even higher than that of virgin PP, while their heat deformation resistance values were found to be similar. Therefore, this unique outcome provides industries, such as the energy and automotive sectors, with the opportunity to substitute PP-rich products with those mostly comprised of a cheaper, more abundant, yet performant PE.