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The aim of the present work is to explore the age-hardening potential of Ti-6Al-4V (Ti-64) alloy with variation of the starting microstructure, with attention to the precipitation of nano-sized Ti3Al phase, as influenced by microstructural features. The alloy was either solution-treated or deformed by compression at temperatures above and below its β-transus to produce microstructures comprising martensitic, lamellar and globular α morphologies, as well as the existence or absence of β phase, and subsequently submitted to ageing treatments at 400°C/8h using in situ x-ray diffraction. Precipitated fractions of Ti3Al were obtained via Rietveld refinement and aged microstructures were characterized by micro-hardness measurements. Results show that α2 precipitation is favored by a globular morphology of α and hindered by a martensitic α morphology, and suggest that the presence of β phase also has as influence on precipitation.