The characterization of Mg-Co-Zr tri-layer stacks using X-ray fluorescence induced by X-ray standing waves, in both the grazing-incidence (GI) and the grazing-exit (GE) modes, is presented. The introduction of a slit in the direction of the detector improves the angular resolution by a factor of two and significantly improves the sensitivity of the technique for the chemical characterization of the buried interfaces. By observing the intensity variations of the Mg Kα and Co Lα characteristic emissions as a function of the incident (GI mode) or detection (GE mode) angle, it is shown that the interfaces of the Si/[Mg/Co/Zr] × 30 multilayer are abrupt, whereas in the Si/[Mg/Zr/Co] × 30 multilayer a strong intermixing occurs at the Co-on-Zr interfaces. An explanation of this opposite behavior of the Co-on-Zr and Zr-on-Co interfaces is given by the calculation of the mixing enthalpies of the Co-Mg, Co-Zr and Mg-Zr systems, which shows that the Co-Zr system presents a negative value and the other two systems present positive values. Together with the difference of the surface free energies of Zr and Co, this leads to the Mg/Zr/Co system being considered as a Mg/CoxZry bi-layer stack, with x/y estimated around 3.5.