Multi-material additive manufacturing enables combining the properties of different materials to produce high-performance functional parts. In this study, a multi-material composed of CuZr-based metallic glass (MG) and the conventional Ti-6Al-4V alloy was synthesized by laser powder bed fusion (L-PBF). MGs are amorphous materials characterised by glass transition. These feature outstanding strength but extremely limited tensile plasticity, while commercially available Ti-6Al-4V alloys can effectively arrest crack propagation due to high toughness. The interface between the two materials is defined by a transition zone consisting of new phases and affecting the performance of the multi-material. According to X-ray diffraction analysis, the additively manufactured MG samples consist mainly of an amorphous phase with a noticeable fraction of crystalline phases, while the Ti-6Al-4V samples consist of the hcp-Ti phase. It was found that the volume fraction of the crystalline phases depends on the LPBF processing parameters. According to the energy dispersive X-ray analysis, microalloying of MG region with the elements from Ti-6Al-4V and vice versa was detected at the interface, resulting in the formation of new phases at the interface. The electron backscatter diffraction analysis suggests that the interface composes predominately of amorphous and bcc-Ti phases. This can be explained by Cu microalloying in the interfacial layer that stabilises the formation of the bcc-Ti phase. Crack propagation analysis indicated that the cracks originated on the surface of the MG region near the interface and propagated through the interface, being arrested and blunted in the Ti-6Al-4V region. The resulting bimetallic composite can be used as a promising material for various applications requiring high strength and toughness along with an excellent corrosion resistance.