The decrease of superplastic forming temperature and improvement of post-forming mechanical properties are important issues for titanium-based alloys. Ultrafine-grained and homogeneous microstructure are required to improve both processing and mechanical properties. This study focuses on the influence of 0.01–2 wt.% B (boron) on the microstructure and properties of Ti-4Al-3Mo-1V (wt.%) alloys. The microstructure evolution, superplasticity, and room temperature mechanical properties of boron-free and boron-modified alloys were investigated using light optical microscopy, scanning electron microscopy, electron backscatter diffraction, X-ray diffraction analysis, and uniaxial tensile tests. A trace addition of 0.01 to 0.1 wt.% B significantly refined priorβ-grains and improved superplasticity. Alloys with minor B and B-free alloy exhibited similar superplastic elongations of 400–1000% in a temperature range of 700–875 °C and strain rate sensitivity coefficientmof 0.4–0.5. Along with this, a trace boron addition provided a stable flow and effectively reduced flow stress values, especially at low temperatures, that was explained by the acceleration of the recrystallization and globularization of the microstructure at the initial stage of superplastic deformation. Recrystallization-induced decrease in yield strength from 770 MPa to 680 MPa was observed with an increase in boron content from 0 to 0.1%. Post-forming heat treatment, including quenching and ageing, increased strength characteristics of the alloys with 0.01 and 0.1% boron by 90–140 MPa and insignificantly decreased ductility. Alloys with 1–2% B exhibited an opposite behavior. For the high-boron alloys, the refinement effect of the priorβ-grains was not detected. A high fraction of borides of ~5–11% deteriorated the superplastic properties and drastically decreased ductility at room temperature. The alloy with 2% B demonstrated non-superplastic behavior and low level of strength properties; meanwhile, the alloy with 1% B exhibited superplasticity at 875 °C with elongation of ~500%, post-forming yield strength of 830 MPa, and ultimate tensile strength of 1020 MPa at room temperature. The differences between minor boron and high boron influence on the grain structure and properties were discussed and the mechanisms of the boron influence were suggested.