Drawing inspiration from the intricacies of nacre structure, Ti2AlNb/Ti6Al4V layered metal composite was fabricated by vacuum hot pressing and achieved high fracture toughness. The fracture toughness of the composite registers at 48.5 MPa∙m1/2, surpassing the theoretical fracture toughness calculated based on the rule of mixture (ROM) and exhibiting 54 % improvement compared toTi2AlNb alloy. The introduction of a layered configuration imparts complex crack propagation pathways to the composite. The occurrences of crack deflection, crack bridging, crack passivation, and interface delamination serve to increase the resistance to crack propagation. Moreover, the plastic deformation of the ductile Ti6Al4V layer and the large plastic zone size of the crack tip can release the stress concentration and delay the fracture of the composite. This understanding not only advances our comprehension of the toughening mechanisms but also has practical implications for the application and development of layered Ti2AlNb alloys.