Three types of solution treatment and aging were designed to reveal the α’ decomposition and its effect on the mechanical properties of near-α Ti-80 alloy, as follows: solution at 970 °C then quenching (ST), ST + aging at 600 °C for 5 h (STA-1), and ST + aging 600 °C for 24 h (STA-2). The results show that the microstructures of the ST samples were mainly composed of equiaxed α_p and acicular α’, with a large number of dislocations confirmed by the KAM results. After subsequent aging for 5 h, α’ decomposed into acicular fine α_s and nano-β (intergranular β, intragranular β) in the STA-1 specimen, which obstructed dislocation motion during deformation, resulting in the STA-1 specimen exhibiting the most excellent yield strength (1012 MPa) and maintaining sufficient elongation (8.1%) compared with the ST (898 MPa) and STA-2 (871 MPa) samples. By further extending the aging time to 24 h, the size of acicular α_s and nano-β gradually increased while the density of dislocations decreased, which resulted in a decrease in strength and an increase in plasticity. Based on this, a microstructures–properties correlation model was proposed. This study provides a new method for strength–plasticity matching of near-α titanium alloys through α’ decomposition to acicular α_s+nano-β.