To produce a tough material for application demanding high impact resistance and low moisture absorption, melt blending of Nylon12 (Polyamide 12, PA12) and natural rubber (NR) was carried out in a brabender plasticorder at 210 °C with rotor speed of 70 rpm in the presence of polystyrene/maleated natural rubber (PS/MNR) blend as a compatibilizer. The effect of compatibilizer content (1, 3, 5, 7 and 10 phr) on phase morphology, thermal, and mechanical properties of [Nylon12/NR]/[PS/MNR] blends was investigated by using SEM, DSC, and Izod impact tester, respectively. The result revealed that PS/MNR blend improved the compatibility of Nylon12/NR blends efficiently due to the presence of amide linkage at the interfaces from the reaction between the reactive groups of MNR and the NH2 end groups of Nylon12 during mixing. A fine phase morphology (good dispersion and small dispersed phase size of NR domains in Nylon12 matrix) of [Nylon12/NR]/[PS/MNR] blends was observed at the optimum compatibilizer content of 7 phr, relating to the improvement of mechanical property. The impact energy of [Nylon12/NR]/[PS/MNR] blends was 503 J/m higher than that of neat Nylon12 (115 J/m) and Nylon12/NR binary blend (241 J/m) due to the toughening effect of rubber and proper morphology. The melting temperature of all blends did not change obviously from thermal analysis. However, the presence of rubber particle obstructed the crystallization of Nylon12 phase, leading to the decreasing of %crystallinity from 93% to around 70%.