Thermal properties and dispersive capacity of diffractive optical elements were expounded in this paper, and the conclusion that optothermal expansion coefficient of diffractive optical element is independent of refractive index of the material was derived. The design method to athermalize the hybrid infrared optical system was studied, a new hybrid system with diffractive surface was structured on the foundation of refractive/reflective optical system using optical design software ZEMAX, and the surface was simulated by MATLAB. The image quality was improved obviously compared with the one without diffractive surface. The system worked at 3.7~4.8μm band with its’ effective focal length of 70mm, field of view of 2° and possessed better athermal performance in the temperature range -40°~+60°. The image quality achieved diffractive limit, besides, a compact structure, small volume and light weight were other advantages of the hybrid system.