The development and application of glow discharge emission spectrometry (GDOES), and the MRI model for quantitative sputter depth profiling are introduced. The measured high-resolution GDOES depth profiles of SiO2 layer naturally grown on the substrates, single thiourea molecular layer and optical multilayer of Mo/B4C/Si are quantitatively evaluated. The layered structure, interface roughness and sputtering rate are obtained accordingly. Meanwhile, the depth resolution values of the GDOES and SMIS depth profiles of Mo/Si multilayers are compared. Finally, the future development of GDOES and the MRI model are prospected.