A novel multilayer diffractive optical element (MLDOE) composed with different optical materials is investigated and the materials combination principle is discussed. The results show that the first layer, the last layer and the middle layer should be high refractive index and low dispersion optical material, low refractive index and high dispersion optical material, and smaller Abbe number optical material, respectively. The diffractive efficiency of the MLDOE at each wavelength in designed band is larger than 90% and the full angle of view can reach 110°, which can effectively improve energy utilization ratio and image quality of the hybrid refractive-diffractive optical system.