Complementary analysis techniques are applied in this work to study the interface structure of Mo/Si multilayers. The samples are characterized by grazing incident x-ray reflectivity, x-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and extreme ultraviolet reflectivity. The results indicate that the layer thickness is controlled well with small diffusion on the interface by forming MoSi2. Considering MoSi2 as the interface composition, simulating the result of our four-layer model fits well with the measured reflectivity curve at 13.5 nm.