A bio-compatible Ti-25 wt% Nb alloy fabricated from a blend of pure elemental powders using laser powder bed fusion additive manufacturing technique. The present work investigated the effects of processing conditions on the evolution of microstructures and its consequential material attributes, such as mechanical properties and corrosion performance. Thermal management strategies comprising laser powers of 200 W and 300 W in complement with a shorter scan length (1 mm) and substrate preheating above β-transus temperature (1123 K) were considered to achieve complete dissolution of niobium particles. The microstructure in the 200 W sample showed thin α′′ martensite needles in β matrix while martensite laths in the 300 W condition appear coarse and were twice the area fraction compared to that in 200 W build. On the other hand, microstructures in the heated substrate sample exhibited the evolution of α and β phases. A multi-scale finite element method based thermo-kinetic model spanning from melt pool scale to the component scale was incorporated to understand the mechanism of the evolution of microstructures during liquid–solid and solid–solid state transformation. Electrochemical performance in the simulated body fluid of the printed alloys was found to be significantly affected by the presence of martensite fractions. Both mechanical and corrosion behaviors were favorably influenced by adoption of the substrate preheating during additive manufacturing due to promotion of diffusional transformation of β to α at the expense of martensitic transformation.