Abstract: A novel multifunctional hybrid oligomer(MEVO) containing both epoxy and vinyl ester group was synthesized using N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenyl methane(TGDDM) and acrylic acid(AA) as raw materials. Three curing systems, MEVO-MEKP, MEVO-MeTHPA and MEVO-MEKP-MeTHPA were prepared by blending MEVO with the initiator methyl ethyl ketone peroxide(MEKP), and the epoxy curing agent methyl tetrahydrophthalic anhydride(MeTHPA). The curing reaction was investi-gated by nonisothermal DSC and FT-IR. Reaction apparent activation energy of each system were calculated. Results showed that vinyl ester cured by free radical polymerization mechanism and had no effect on epoxy group in MEVO-MEKP. Vinyl ester thermal cured in the process of epoxy curing in MEVO-MeTHPA. Vinyl ester and epoxy group cured according to respective mechanism and influenced each other in MEVO-MEKP-MeTHPA.