Ti-45Al-8Nb alloy is widely utilized in the lightweight design of the aerospace field because of its excellent properties. In order to make full use of this alloy, it is important to carry out relevant research, such as into the joining process of Ti-45Al-8Nb alloy. In this work, Ti-45Al-8Nb alloys were successfully connected by a TiZrCuNi amorphous interlayer, which was fabricated using the rapid solidification method. Ti-45Al-8Nb joints were composed of two zones. The typical microstructure of a Ti-45Al-8Nb joint was Ti-45Al-8Nb/AlCuTi + Ti3Al/(Ti, Zr)(Cu, Ni) + (Ti, Zr)2(Cu, Ni)/Ti3Al + AlCuTi/Ti-45Al-8Nb. The diffusion of elements between the interlayer and the substrate was enhanced by increasing the brazing temperature, which resulted in an increase in the thickness of the interfacial reaction layer. The maximum shear strength was 171.2 MPa, which was obtained at 930 °C. The typical cleavage fracture was found in all of the Ti-45Al-8Nb joints. The mechanical properties of the joint were compromised at high brazing temperature due to the presence of excessive (Ti, Zr)2(Cu, Ni) phase and coarse Ti3Al phase, both of which are inherently brittle and harmful to the shear strength of the obtained joint.