TiC layers were formed by the low-pressure chemical vapour deposition (LPCVD) technique on tool carbon steel (0.9 wt % C; 0.4 wt % Si; 0.5 wt % Mn), bare or nitrided by glow discharge with formation of zones consisting of (epsilon + gamma’) and (gamma’) phases. The composite TiN-TiC layers were formed by the deposition of TiN on the coated TiC layers, by a pressure-assisted chemical vapour deposition (PACVD) technique or by TiC sputtering in nitrogen under glow discharge conditions. The electrochemical behaviour of the metal/coating has been established by potentiodynamic tests done in acid (20% H3PO4) and alkaline (0.1 N NaOH) solutions. The deposited layers protect the steel by decreasing the steel area exposed to the aggressive solution and by promoting steel passivation. The protective ability of composite TiN/TiC layers is higher than that of corresponding single layers. Improvement of the protective ability of LPCVD TiC layers is achieved by the deposition conditions, providing the formation of fine grains [111] texture. The electrochemical behaviour of steel coated with complex TiN/TiC layers approaches the intrinsic electrochemical behaviour of TiN.