Magnetron sputtering has been employed for several decades to produce protective and multi-functional coatings, thanks to its versatility and ability to achieve homogeneous layers. Moreover, it is suitable for depositing coatings with very high melting points and that are thermodynamical unstable, which is difficult to accomplish by other techniques. Among these types of coating, transition metal (Me) carbides/nitrides (MeC/N) and amorphous carbon (a-C) films are particularly interesting because of the possibility of tailoring their properties by selecting the correct amount of phase fractions, varying from pure MeN, MeC, MeCN to pure a-C phases. This complex phase mixture can be even enhanced by adding a fourth element such Ag, Pt, W, Ti, Si, etc., allowing the production of materials with a large diversity of properties. The mixture of phases, resulting from the immiscibility of phases, allows increasing the number of applications, since each phase can contribute with a specific property such as hardness, self-lubrication, antibacterial ability, to create a multifunctional material. However, the existence of different phases, their fractions variation, the type of transition metal and/or alloying element, can drastically alter the global electrochemical behaviour of these films, with a strong impact on their stability. Consequently, it is imperative to understand how the main features intrinsic to the production process, as well as induced by Me and/or the alloying element, influence the characteristics and properties of the coatings and how these affect their electrochemical behaviour. Therefore, this review will focus on the fundamental aspects of the electrochemical behaviour of magnetron-sputtered films as well as of the substrate/film assembly. Special emphasis will be given to the influence of simulated body fluids on the electrochemical behaviour of coatings.