Solute decoration at grain boundaries (GB) leads to a number of phenomenon such as changes in interface structure, mobility, cohesion etc. Recent experimental investigations on interfacial segregation in steels are based on microstructural characterisation using two correlative methodologies, namely, Transmission Electron Microscopy-Atom Probe Tomography (APT) and Electron Backscatter Diffraction-APT. Considering the growing interest in this avenue, the present review is aimed at addressing the common adsorption isotherms used for quantifying interfacial segregation and providing an overview of the present state of experimental research in the area of GB segregation in steels. The areas where an understanding of GB segregation may be utilised have also been highlighted with a focus on the experimental challenges associated with understanding GB segregation in steels.