In the present work, the effects of ageing treatment on the microstructures of a near-β Ti alloy (TC18) are studied. The influence of ageing treatment on the tensile properties and failure mechanisms are systematically analyzed. It is found that the size and morphology of the primary α (αp) phases are insensitive to ageing temperature and time. Furthermore, the ageing temperature and time dramatically influence the precipitation of the secondary α (αs) phases. Massive αs phases precipitate and gradually coarsen, and finally weave together with increasing the ageing temperature or extending the ageing time. The thickness of αs phases is responsible for the material strengths, while the content of α phases can enhance the material ductility. The ductile characteristics of the alloy with coarser αs phases are more obvious than those with thinner αs phases. Therefore, the ageing treatment is helpful for the precipitation and homogeneous distribution of αs phases, which is essential for balancing the strengths and ductility of the studied Ti alloy.