Grazing incidence X-ray reflectivity (GIXRR) and X-ray fluorescence (GIXRF) are complementary techniques for the characterization of layered materials. It is shown that the analysis of multilayers by this combined technique can overcome the deficiencies of individual techniques. In this study, Si(sub)/W/Ni/Ti/Ni was studied using grazing incidence X-ray reflectivity and X-ray fluorescence. It is suggested that the geometrical factor correction in GIXRF analysis can be avoided by using the intensity ratio of the fluorescence yields from Ni-Kα and Ti-Kα. Additionally, the fluorescence intensity of Ni-Kα, Ti-Kα, Si-Kα and the elastic scattering are analyzed quantitatively with the corresponding GIXRR profile to obtain reliable structural parameters about the sample.