Additive manufacturing (AM) offers a radical net-shape manufacturing approach for titanium aluminide alloys but significant challenges still remain. A study has been made of the AM of a high niobium-containing titanium aluminide alloy (Ti–45Al–7Nb–0.3W, in at% throughout the paper) using selective electron beam melting (SEBM). The formation of various types of microstructural defects, including banded structures caused by the vaporization of aluminum, was investigated with respect to different processing parameters. To avoid both micro- and macro-cracks, the use of higher preheating temperatures and an intermediate reheating process (to reheat each solidified layer during SEBM) was assessed in detail. These measures enabled effective release of the thermal stress that developed during SEBM and therefore the avoidance of cracks. In addition, the processing conditions for the production of a fine full lamellar microstructure were identified. As a result, the Ti–45Al–7Nb–0.3W alloy fabricated showed outstanding properties (compression strength: 2750 MPa; strain-to-fracture: 37%). SEBM can be used to fabricate high performance titanium aluminide alloys with appropriate processing parameters and pathways.