MgO-based cementitious materials have attracted increasing attentions due to their advantages of low energy consumption, fire resistance, and low CO2 emission. This study develops a new reactive MgO cement (RMC)-silica fume (SF) engineered cementitious composite (ECC). The effects of RMC∶SF mass ratio, fiber type, fiber content, and curing conditions on the mechanical properties and strain-hardening behavior of the RMC-SF ECC are investigated. The hydration characteristics of RMC-SF ECC under different curing conditions were studied through X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) analysis. It was found that the RMC-SF ECC obtained a tensile strain capacity of 5.7%. Polyethylene (PE) fibers achieved higher compressive strength, and polyvinyl alcohol (PVA) fibers yielded better tensile strain capacity. A RMC-SF mass ratio of 1∶1 obtained a higher ductility under high temperature curing at 50°C. Although carbon dioxide curing improves the mechanical properties of RMC-SF ECC due to the formation of MgCO3, it greatly reduces its ductility. A large amount of brucite and M─ S─ H gels were generated under room temperature curing with plastic wrap.