Ti3SiC2 ceramic and TC4 alloy were successfully joined by a contact-reactive brazing technique using Ti/Ni/Ti interlayers. The results showed that the typical interfacial microstructure of the TC4/Ti3SiC2 joint obtained at 1000 °C for 10 min was TC4/α-Ti + β-Ti + Ti2Ni/Ti2Ni + Ti3AlC + Ti5Si3Cx + TiC/Ti3SiC2. The width of the brazing seam increased and the content of Ti2Ni phase decreased with increased brazing temperature and brazing time. Large amount of Ti2Ni phase distributed in the joint brazed at 980 °C. The joint brazed at 1000 °C for 10 min was well bonded, and the maximum shear strength, 82 MPa, was obtained in corresponding joint and the fracture occurred mainly in the Ti3SiC2 substrate. When the brazing temperature was further elevated, a large number of voids appeared at the interface between the TC4 alloy and the brazing layer, and the shear strength dramatically decreased. Moreover, the formation mechanism of the brazed joints is discussed.