In the field of additive manufacturing (AM), a promising alloy that is gaining attention is the near-α Ti-6Al-2Sn-4Zr-2Mo (Ti6242) alloy. This alloy is known for its remarkable resistance to creep and corrosion at elevated temperatures. However, the production of Ti6242 components via Laser-based AM technologies faced with several challenges, such as the formation of residual stress in the as-built state that originates from the nature of these processes. Therefore, this study has a dual objective: first, to evaluate the microstructure and residual stresses in the as-built Ti6242 produced through laser powder bed fusion. Secondly, to investigate the impact of a promising post heat treatment on mitigating residual stresses, inducing alterations in the microhardness of the Ti6242 alloy and its ductility, phase transformations and microstructure evolution. The as-built specimen exhibited a significant residual stress of 1357 MPa, which was caused by the pronounced temperature gradients experienced during the fabrication process. It is interesting to note that this promising post heat treatment was highly effective in eliminating 99% of the residual stress. After heat treatment, the amount of α' present in the as-built specimen decreased. This resulted in the activation of diffusion of elements such as molybdenum, causing a proportion of the α' to decompose into the more ductile α+β structure. Additionally, it is revealed that the microstructural changes and relieved stresses from the heat treatment process caused a lower microhardness and a higher ductility under compressive loading, as the elongation and toughness reached 20.5% and 23.255 kJ/mm3 in the heat-treated samples, respectively. The outcomes of this work facilitate the use of this alloy in the production of complex shape components through laser-based AM technologies.