The microstructure, phase composition, hardness, and tensile properties of the Ti-48Al-2Cr-5Nb alloy have been systematically investigated using laser additive manufacturing technology. Results indicate that both the as-deposited and annealed microstructures contain both the α2 (Ti3Al) and γ (TiAl) phases. As the annealing temperature increased, the structure changed significantly from a large block structure to a fine equiaxed structure and finally to a large lamellar structure. Nevertheless, the amount and distribution of precipitation of α2 phase are obviously different, especially during the annealing at 1260 °C, where the fine α2 phases are evenly distributed on the γ phase matrix. The hardness value of the as-deposited sample is the highest, with a HV value of 484 at the room temperature, while the hardness value of the annealed sample at 1260 °C is the smallest, with a HV value of 344. An annealed sample at 1260 °C exhibits the highest tensile strength and elongation at room temperature, with values of 598 MPa and 2.1%, respectively. These values are increased by 1.15 times and 1.4 times compared to the as-deposited sample (519 MPa, 1.5%).