Metal additive manufacturing processes induce residual stress in as-built components. These residual stresses are detrimental to part quality as they can induce defects such as warping and delamination. In some cases, when complex components are built, residual stress can even cause a build job to fail due to the recoater crashing into the distorted part. In this paper, the residual stress values of Ti6Al4V and Ti-6Al-2Sn-4Zr-6Mo alloys were evaluated by the cantilever approach and by the X-ray diffraction sin²(Ψ) method. The results showed that, as expected, Ti6Al4V as-built cantilevers displayed high distortion and von Mises equivalent stress values up to 494 MPa. On the contrary, as-built Ti-6Al-2Sn-4Zr-6Mo cantilevers were characterized by almost null warping and a residual stress value in the as-built state of 191 MPa. This different behavior is mainly due to the different properties of the hexagonal α’ martensite in Ti6Al4V and the soft orthorhombic α’’ martensite in Ti6246. The post-processing heat treatment significantly reduced the residual stress in Ti6Al4V, lowering it to 44 MPa, while, in the case of Ti-6Al-2Sn-4Zr-6Mo, the post-processing heat treatment did not affect the residual stress conditions. These findings suggest that Ti-6Al-2Sn-4Zr-6Mo could be a suitable candidate for the additive manufacturing production of extremely complex parts, as it could reduce the risks associated with recoater crashes and job failures.