In this paper, we propose to explore the infrared (IR) behavior of multilayer diffractive optical elements (MLDOEs). IR MLDOEs are designed for the development of space instruments dedicated to Earth observation. The phase effect of the MLDOE on a paraxial plane wave is studied using exact kinoform shapes for each layer. The modeling of the optical path difference uses thin element approximation. Until now, MLDOEs have been designed and simulated on ray-tracing software with binary diffractive layers. In this study, after passing through the MLDOE, the field is propagated using a method that utilizes the angular spectrum of plane waves. The Strehl ratio is used to determine the “best focus” plane, where it is shown that the focalization efficiency is above 95% for the working order in the mid- and long-wave IR bands. This result, along with the very low energy content of the other orders, proves the strong imaging potential of MLDOEs for dual-band applications. It is also demonstrated that the MLDOE has the same chromatic behavior as standard DOEs, making it a very useful component for IR achromatization.