ABSTRACT To tackle the challenge of non‐destructively analyzing complex oxide layers formed by atmospheric corrosion on active metals, we investigate the potential of inverse spatially offset Raman spectroscopy (inverse‐SORS) to detect corrosion products and elucidate how the spectroscopic features of SORS vary. This study explores the utilization of inverse‐SORS technology for longitudinal structural analysis of opaque CeO 2 /La 2 O 3 laminates, which serve as a proxy for corrosion products. Through a combination of experimental measurements and Monte Carlo simulation, it demonstrates the feasibility of inverse‐SORS in non‐destructively elucidating the layered structure of these laminates. With increasing the spatial offset of this technology, the Raman intensity ratio of La 2 O 3 ‐to‐CeO 2 increases from 0.23 to 3.2 and then decreases to 0.27 for the CeO 2 /La 2 O 3 sample with a 34‐μm‐thick CeO 2 layer under 532‐nm excitation, whereas the bottom La 2 O 3 layer is hardly detected when the thickness of the upper La 2 O 3 layer increases to 225 μm. The results reveal that a thinner CeO 2 layer facilitates the escape and detection of Raman signals originating from the bottom La 2 O 3 layer, leading to an enhanced La 2 O 3 ‐to‐CeO 2 signal ratio and a reduced offset at the characteristic peak. The research also sheds light on the intricate interplay among multiple variables, such as spatial offset, laser wavelength, the corresponding absorption factor, the thickness of the oxide layer, and the compactness. These insights suggest that SORS is a valuable and non‐destructive approach for dissecting the structures of highly turbid composites of metallic compounds and semi‐quantitatively deducing their thickness.