A Ti-48Al-2Cr-2Nb alloy was prepared by laser directed energy deposition (DED). The microstructure of the DED-produced Ti-48Al-2Cr-2Nb alloy exhibited a coarse columnar structure along the building direction. Through a combination of experiment and numerical simulation, the temperature gradient and solidification rate of the single-track sample were calculated theoretically. The columnar to equiaxed transition (CET) behavior of molten pool solidification was quantitatively analyzed, and the microstructure transition diagram was established. The effect of TiB2 on the microstructure and mechanical properties of the TiAl alloy was investigated. The columnar changed to equiaxed grains in the vertical cross section by adding nanometer-sized TiB2 particles and the microstructure was significantly refined. The grain size was reduced from 48.5 μm to 4.9 μm. Some equiaxed γ grains were distributed around the banded TiB2. The compressive properties were improved from 628.4 MPa to 698.8 MPa by adding nanometer-sized TiB2 particles. Finally, the solidification behavior and the microstructure refinement mechanism caused by the addition of TiB2 particles were discussed.