The phenolic‐type phthalonitrile (PN) was added to EP/DDM system in order to enhance the thermal and mechanical performance at high temperature. The influence of the added PN on the curing process of EP/DDM was studied via DSC and the activating energy (Eα) was calculated based on iso‐conversional method. The Eα values corresponding to EP/DDM crosslink reaction remained at about 60 kJ mol−1 while it dramatically increased to 68.2 kJ mol−1 when PN content reached 50 wt% (EP‐PN50). The Tg and char yield at 700°C in N2 increased from141°C, 25.7%, for the neat EP/DDM to 226°C, 68.7% for the EP‐PN50. The measured char yields of the cured blend were higher than the calculated values which implies the interaction between EP/DDM and polyphthalonitrile network. The tensile and bending tests were carried out at 413 K and the modulus of EP‐PN50 remains 2.3 Gpa. On the meantime, the cyano‐functionalized SiO2 (CNSiO2) was prepared to further promote the mechanical behaviors of this resin blend in high temperature. The contact angles of raw SiO2, KH560SiO2, CNSiO2 with EP‐PN50 are 59.3, 52.6, 49.7°, respectively, which confirms the better wettability of CNSiO2 to the EP/PN blend. Furthermore, the tensile and bending tests conducted at 413 K confirmed that the CNSiO2 was more efficient on enhancing the mechanical performance of this EP/DDM/PN system at high temperature.