Corrosion is a subject of interest to interdisciplinary research communities, combining fields of materials science, chemistry, physics, metallurgy and chemical engineering. In order to understand mechanisms of corrosion and the function of corrosion inhibitors, the reactions at the interfaces between the corrosive electrolyte and a steel surface, particularly at the initial stages of the corrosion process, need to be described. Naturally, these reactions are strongly affected by the nature and properties of the steel surfaces. It is however seen that the majority of recent corrosion and corrosion-inhibition investigations are limited to electrochemical testing, with ex situ analysis of the treated steels (post-exposure analysis). The characterization of materials and their surface properties, such as texture and morphology, are not being considered in most studies. Similarly, in situ investigations of the initial stages of the corrosion reactions using advanced surface characterization techniques are scarce. In this review, attention is brought to the importance of surface features of carbon steels, such as texture and surface energy, along with defects dislocation related to mechanical processing of carbon steels. This work is extended to a critical review of surface analytical techniques used for characterization of carbon steels in corrosive media with particular focus on examining steel surfaces treated with corrosion inhibitors. Further, emerging surface analysis techniques and their applicability to analyse carbon steels in corrosive media are discussed. The importance of surface properties is commonly addressed by surface scientists as well as researchers in other chemistry fields such as nanotechnology, fuel cells, and catalysis. This article is expected to appeal to a broad scientific community, including but not limited to corrosion scientists, material chemists, analytical chemists, metal physicists, corrosion and materials engineers.