Carbon steel coupons were buried in a specific low-pH cement grout designed for radioactive waste disposal and left 6 months in anoxic conditions at 80 °C. The corrosion product layers were analyzed by µ-Raman spectroscopy, XRD, and SEM. They proved to be mainly composed of iron sulfides, with magnetite as a minor phase, mixed with components of the grout. Average corrosion rates were estimated by weight loss measurements between 3 and 6 µm yr⁻¹. Corrosion profiles revealed local degradations with a depth up to 10 µm. It is assumed that the heterogeneity of the corrosion product layer, mainly composed of conductive compounds (FeS, Fe₃S₄, and Fe₃O₄), promotes the persistence of corrosion cells that may lead to locally aggravated degradations of the metal. New cement grouts, characterized by a slightly higher pH and a lower sulfide concentration, should then be designed for the considered application.