β-stabilized Ti-alloys present several unexplored and intriguing surprises in relation to orthorhombic α″ phases. Among them are (i) the diffusion-controlled formation of transitional α″ iso , α″ lean and α″ rich phases and ii) the highly anisotropic thermal expansion of martensitic α″. Using the prototypical Ti-Nb system, we demonstrate that the thermodynamic energy landscape reveals formation pathways for the diffusional forms of α″ and may lead to a stable β-phase miscibility gap. In this way, we derive temperature-composition criteria for the occurrence of α″ iso and resolve reaction sequences during thermal cycling. Moreover, we show that the thermal expansion anisotropy of martensitic α″ gives rise to directions of zero thermal strain depending on Nb content. Utilizing this knowledge, we propose processing routes to achieve null linear expansion in α″ containing Ti-alloys. These concepts are expected to be transferable to other Ti-alloys and offer new avenues for their tailoring and technological exploitation. β-stabilized Ti-alloys provide the basis for a multitude of future applications in biomedicine and aeronautics 1,2. Their low elastic moduli, shape memory and superelastic effects, blended with pronounced hardenability and attractive ductility captivates the attention of engineers and material scientists alike. Despite their seemingly simple phase diagrams β-stabilized systems, such as Ti-Nb (Fig. 1) show a vast array of phase transformations and transient states, attributed to the extensive α-β two-phase field. The ensuing exceptionally pronounced metastability necessitates large diffusional compositional changes and extended aging durations (up to many weeks or months) to reach (meta)stable equilibrium. The nature of compositional fluctuations decisively influences the refinement of precipitation products 3-5 and the β ↔ α″ martensitic transformation 6. For instance, detailed (micro)structural studies uncovered non-conventional transformation pathways for α-precipitation 3,7-9. Of particular note is the discovery of transitional α″-like structures (α″ iso , α″ lean , α″ rich) during martensite decomposition and prior to α precipitation 7-11. Furthermore, recently extraordinarily large anisotropic thermal expansion was revealed in α″ martensite of the Ti-Nb system 9,12. The successful development of novel structural and functional Ti-alloys with bespoke mechanical and shape memory behaviour depends critically on accurate descriptions of precipitation and decomposition processes. In addition, key for dimension critical components is the ability to control thermal expansion 13,14. Nowadays, the core challenge in developing new Ti-alloys lies in unravelling the complexity of phase reactions and in deriving robust thermodynamic and structural descriptions to assist the alloy design process. Empirical trial-and-error methods still prevail today, nevertheless systematic attempts are made to develop and employ predictive capabilities through ab-initio 15-19 , phase-field 20,21 and CALPHAD 22-27 methods. The...