Corrosion inhibitors are one of the best practices to prevent the far-reaching negative impacts of corrosion on ferrous alloys. A thorough understanding of their corrosion-inhibiting effects is essential for a sustainable economy and environment. Anionic surfactants are known to act efficiently as corrosion inhibitors. Here, we present that in-situ atomic force microscopy (AFM) measurements can provide deep insights into the adsorption and inhibition mechanism of surfactants on stainless steel surfaces during local corrosion. These include the configuration of surfactant molecules on the surface and how the microstructure of the stainless steel surface influences the inhibition process. Three different anionic surfactants, namely palm kernel oil (PKO), linear alkylbenzene sulfonate (LAS), and fatty alcohol ether sulfate (FAES), were investigated on a titanium-stabilized ferritic stainless steel (1.4510) in NaCl solution. For PKO, the results show random adsorption of bi- and multilayer whereas LAS and FAES adsorb only as local corrosion occurs. Thereby, LAS accumulates only locally and especially at the titanium precipitates of the 1.4510 and FAES forms a densely packed monolayer on the surface. This leads to better corrosion inhibiting properties for LAS and FAES compared to PKO.