The Cu/Ti3AlC2 composites were fabricated by pressureless sintering a mixture of Ti3AlC2 and copper powders. Their microstructures and properties were investigated. It was found that the molten Cu accelerating the decomposition of Ti3AlC2, inducing the interfacial exfoliation to generate, and forming a sub-micro-layered structure making up of TiCx layers and Cu-Al alloy layers within a Ti3AlC2 grain. The flexural strength of the composites is reduced with the increase of the volume content of Ti3AlC2 from 50 % to 90 %. The highest flexural strength reaches to as high as 915 MPa. The fracture mode was changed from ductile to brittle with increase in the content of Ti3AlC2. The higher flexural strength can be attributed to a stronger interface bond between TiCx and Cu-Al phase. The electrical resistivity and Vickers hardness of the composites were also measured.