Evolution of secondary α phase during aging treatment of a novel near β titanium alloy Ti-6Mo-5V-3Al-2Fe(wt.%) was studied by OM, SEM, and TEM. Results indicated that size and distribution of secondary α phase were strongly affected by aging temperature and time. Athermal ω phase formed after super-transus solution treatment followed by water quenching, and promoted nucleation of needle-like intragranular α in subsequent aging process. When aged at 480 °C, fine scaled intragranular α with small inter-particle spacing precipitated within β grains and high ultimate tensile strength above 1500 MPa was achieved. When the aging temperature increased, the size and inter-particle spacing of intragranular α increased and made the strength reduce, but the ductility got improved. When aging temperature reached as high as 600 °C, ω phase disappeared and intragranular α coarsened obviously, resulting in serious decrease of strength. While mutually parallel Widmanstätten α laths formed at the vicinity of β grain boundaries and grew into the internal area of β grains, and significant improvement of ductility was achieved. As the aging time increased from 4 h to 16 h at 600 °C, the intragranular α grew slightly and brought about minor change of mechanical properties.