This paper deals with the steel/concrete interface of a corroded beam B2CL1 after a 23 years exposure in chloride environment. XRD, SEM and Raman techniques were performed to investigate the chemical compositions and the spatial distribution of corrosion products. The experimental results illustrate that the corrosion product layer is a multi-layer constituted as marbling structure. It is composed of a mix of iron oxides and iron oxi-hydroxides. Iron species were found in the vicinity of concrete mainly in cracks, as it was already observed in the literature.