Mo-Ti3SiC2 layered composite was successfully prepared by spark plasma sintering at 1573 K for 20 min under a pressure of 50 MPa in vacuum. The Mo and Ti3SiC2 layers were metallurgically bound together without noticeable superficial defects and micro-cracks at the interface. The fabricated Mo-Ti3SiC2 layered composite was annealed at 1273 K under vacuum for 5, 10, 20 and 40 h to study the composite’s thermal stability. Three intermediate layers, Mo2C, MoSi2 and Ti5Si3Cx, were formed at the interface. Experimental results showed that the Mo-Ti3SiC2 layered composite prepared in this study has good interfacial stability at elevated temperature.