The interfacial microstructure, interfacial shear properties, and shear fracture morphology of Cu/Al/Cu trilayered composites prepared by high-temperature oxygen-free rolling were studied, and the interfacial shear fracture mechanism was revealed. The results showed that the Cu/Al/Cu trilayered composites have a good metallurgical bonding interface. The interfacial microstructure is composed of Al2Cu, AlCu, and Al4Cu9. The intermetallics (IMCs) parallel to the rolling direction show discontinuous distribution, while the IMCs perpendicular to the rolling direction have mainly continuous distribution and occasional discontinuous distribution. The interfacial shear strength at room temperature can reach 68 MPa, and when the test temperature rises to 350 °C, the interfacial shear strength drops sharply to 16.9 MPa. The interfacial shear fracture mainly occurs in the low-strength Al layer due to the good metallurgical bonding interface. The IMCs near the shear fracture exhibit clear signs of cracking, and there is a phenomenon where the Cu layer embeds into the Al layer in a "sawtooth" shape. Meanwhile, shear fracture also occurs in the IMCs layer, and a small amount of Al will attach to the surface of the IMCs. However, the high bonding strength resulting from the excellent metallurgical bonding of the interface makes this type of shear fracture rare. The shear fracture of Cu/Al/Cu trilayered composites is mainly dominated by the fracture of the low-strength Al layer and the occasional fracture of the IMCs.