Laser powder deposition was applied to fabricate the Ti–6.5Al–3.5Mo–1.5Zr–0.3Si(wt%)/Ti–47Al–2Cr–2Nb–0.2W–0.15B(at%) bi-material system. The asdeposited TC11 alloy shows a basket-wave-like morphology while the as-deposited c-Ti Al alloy consists of fully a2/c lamellar microstructures. Regarding the thermal mismatch between TC11 and c-Ti Al during processing, the interface microstructure evolution was concerned. The transformation pathway was illustrated. It is found that the content changes of Al elements and b-stabilizers Mo, Cr,and Nb are responsible for the evolution of microstructures at the interface. The fracture surfaces are located at the c-Ti Al side. The bi-material shows a brittle-fracture manner, with the ultimate tensile strength of 560 MPa. Laser powder deposition was applied to fabricate the Ti-6.5Al-3.5Mo-1.5Zr-0.3Si (wt%) / Ti-47Al-2Cr-2Nb-0.2W- 0.15B (at%) bi- material system. TC11 alloy shows a basket-wave-like morphology while the as-deposited c-Ti Al alloy consists of fully a2 / c lamellar microstructures. Regarding the thermal mismatch between TC11 and c-Ti Al during processing, the interface microstructure evolution was concerned. The transformation pathway was illustrated. It is found that the content changes of Al elements and b-stabilizers Mo, Cr, and Nb are responsible for the evolution of microstructures at the interface. The fracture surfaces are located at the c-Ti Al side. The bi-material shows a brittle-fracture manner, with the ultimate tensile strength of 560 MPa.