The oxide scales of AISI 304 formed in boric acid solutions at 300°C and pH = 4.5 have been studied using X-ray photoelectron spectroscopy (XPS) depth profiling. The present focus is depth profile quantification both in depth and chemical composition on a molecular level. The roughness of the samples is studied by atomic force microscopy before and after sputtering, and the erosion rate is determined by measuring the crater depth with a surface profilometer and vertical scanning interferometry. The resulting roughness (20–30 nm), being an order of magnitude lower than the crater depth (0.2–0.5 μm), allows layer-by-layer profiling, although the ion-induced effects result in an uncertainty of the depth calibration of a factor of 2. The XPS spectrum deconvolution and data evaluation applying target factor analysis allows chemical speciation on a molecular level. The elemental distribution as a function of the sputtering time is obtained, and the formation of two layers is observed—one hydroxide (mainly iron–nickel based) on top and a second one deeper, mainly consisting of iron–chromium oxides.