FeCo/Si is a promising material combination for polarized neutron supermirrors because of its appropriate optical constants. Five FeCo/Si multilayers with monotonically increasing FeCo layer thicknesses were fabricated. Grazing incidence x-ray reflectometry and high-resolution transmission electron microscopy were performed to characterize the interdiffusion and asymmetry of the interfaces. Selected area electron diffraction was used to determine the crystalline states of FeCo layers. It was found that the asymmetric interface diffusion layers existed in FeCo/Si multilayers. Furthermore, the FeCo layer started the transition from amorphous to crystalline when the thickness of the FeCo layer reached 4.0 nm.