The electrochemical behavior of low alloyed Fe-Cr steels with 3 and 5% wt. of Cr in neutral Na2SO4 electrolyte combined with a detailed chemical and morphological characterization of these alloys performed by Auger electron spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry and scanning electron microscopy are presented here. The corrosion of low alloyed Fe-Cr steels proceeds in the prepassive range, with the formation of corrosion surface films having a duplex structure with outer iron oxide/hydroxide layer and inner Cr oxide-rich layer. The thickness, composition, and the morphology of the surface films vary as a function of chromium content in the alloy as well as conditions of electrochemical tests (temperature). Even a low chromium content shows a beneficial effect on the corrosion performances of the Fe-Cr steels. The chromium as a more active component than iron of ferrite increases the anodic activity of this phase, which results in a rapid saturation of the surface with the anodic reaction products forming a fine crystalline-like and compact layer of corrosion products. In this way, the chromium acts as a modifier of formation/crystallization of the iron-rich surface film (mainly magnetite) in the prepassive range.