For the first time, additive manufacturing was used to obtain a strong joint (bonding strength >200 MPa) between stainless steel and Ti-6Al-4V using a V interlayer. The V interlayer applied via solid-state joining prevented the formation of brittle intermetallic phases more effectively than a V interlayer deposited by a liquid-state process. The microstructure and strength of the joint interface depended on the laser power and scan speed. The joint strength decreased with increasing annealing time, especially after 4 and 24 h, demonstrating the presence of the Fe-V-Cr σ-phase.