The objective of this research was to improve the compatibility between Natural Rubber/Polypropylene NR/PP blends through physical and chemical compatibilization methods. The physical compatibilization involved the use of epoxidized natural rubber/maleic anhydride-grafted polypropylene (ENR50/PP-g-MA) as a dual compatibilizing agent (CA50), while the process of reactive compatibilization entailed chemically modifying NR and PP phases through the grafting maleic anhydride (MA). Several formulations were prepared by melt mixing using a Brabender plasti-corder. The effects of physical and chemical compatibilization on the technical properties were investigated. FTIR analysis revealed the emergence of two distinctive peaks corresponding to the CO group of MA grafted onto PP and NR chains. FTIR analysis has also confirmed the taking place of reactions between the polar functional groups of PP-g-MA and ENR50. The rheological properties indicated that the viscosity of the NR-g-MA/PP-g-MA is lower than those of the control blend and CA50-based NR/PP system. The mechanical and dynamic mechanical findings corroborated the improvement of interfacial adhesion between NR/PP phases, especially for the NR/PP/CA50 system. SEM examination demonstrated a more uniform dispersion of the PP phase in the CA50-based NR/PP, compared to the control blend and NR-g-MA/PP-MA. NR-g-MA/PP-g-MA exhibits greater miscibility and interaction potential compared to the control NR/PP, and less than NR/(ENR50/PP-g-MA)/PP system. DFT calculations further validate the effect of compatibilization methods on TPE blends. Specifically, Quantum molecular descriptors revealed the role of ENR50/PP-g-MA as an intermediary in facilitating compatibility between NR/PP. These findings indicate that the physical compatibilization method approach using ENR50/PP-g-MA as a dual compatibilizer is a potential compatibilizer for NR/PP.