We demonstrated a method of fabricating thermosetting epoxy polymer with shape memory effect modified Poly (ether ether ketone) (6F-PEEK) based on the formation of a phase-segregated morphology. The peculiarities of shape memory effects of the epoxy resin modified by 6F-PEEK were investigated. DMA result showed two glass transition temperatures in this blended material. The cured epoxy phase showing high Tg of 223°C acted as hard-segment-forming phase the and was responsible for the permanent shape. The 6F-PEEK can be used as switching phase for a thermally induced shape-memory effect. The transition temperature (Ttran) was 150°C, which was between the T g of cured epoxy and 6F-PEEK. At the special concentrations of 6F-PEEK, the shape memory effect accompanied by a significant increase in volume was observed. The highest shape memory effect was obtained for the blended material with 25.00 wt% of 6F-PEEK. The shape retention rates and the shape recovery rates were 96-99% and 100%, respectively. The times of shape-recovery were all defined in 2 min. The mechanism of shape memory effects and the mechanical properties of the cured resin were discussed.