The electrochemical corrosion behaviors of Ti 3 SiC 2 /Cu composite and polycrystalline Ti 3 SiC 2 in a 3.5% NaCl medium were investigated by dynamic potential polarization, potentiostat polarization, and electrochemical impedance spectroscopy. The polycrystalline Ti 3 SiC 2 was tested on the identical condition as a control. The characterizations of XRD, X-ray photoelectron spectroscopy, scanning electron microscope, and energy-dispersive spectrometer were used to study the relevant passivation behavior and corrosive mechanism. The self-corrosion current density of Ti 3 SiC 2 /Cu (6.46 × 10 −6 A/cm 2 ) was slightly higher than that of Ti 3 SiC 2 (1.64 × 10 −7 A/cm 2 ). Under open circuit potential, the corrosion resistance of Ti 3 SiC 2 /Cu was better than that of Ti 3 SiC 2 . Ti 3 SiC 2 /Cu exhibited a typical passivation feature with a narrow passivation interval and a breakdown phenomenon. The better corrosion resistance of Ti 3 SiC 2 was due to the more stable Si layer of the former. In comparison, for Ti 3 SiC 2 /Cu composites, Cu reacted with the reactive Si layers in Ti 3 SiC 2 to form Cu-Si compounds and TiC, destroying the weak interaction between Si layers and Ti-C layers. In the other hand, the as-formed Cu-Si compounds and TiC dissolved during the corrosion of Ti 3 SiC 2 /Cu in the 3.5% NaCl medium, causing to the destruction of the passivation film on its surface.