The use of organic coatings in conjunction with cathodic protection (CP) for buried structures is the usual method for protecting steel against corrosion. When the organic coating loses its protective ability, regardless of the reason, the CP becomes the active protection, leading to a specific local environment. This environment can be characterized by high alkalinity, which can be detrimental for the coated structure, either by weakening the steel–coating interface or by the chemical aging of the coating. Thus, the coating must be compatible with CP and able to sustain aging under an alkaline environment. In this study, the susceptibility to alkaline aging and its consequences in regards to coating performance have been investigated for two commercial coatings used for buried structures—fusion bonded epoxy (FBE) and liquid epoxy (LE)—in free membrane and coated steel configurations. The results showed a clear impact of alkaline aging on the studied LE, leading to a significant reduction in coating resistance and ultimately, failure of the steel–coating interface, whereas the studied FBE remained stable. The presented results relate to a precise formulation of LE and FBE; however, the proposed chemical method appears to be relevant and shows the necessity of considering such specific aging results for coating specifications and improvements.