The work is aimed at the study of the formation and refinement of microstructure appearing in the solidifying refractory TiAl-based intermetallics being inoculated with precise boron addition. The novelty of research consists in test application of lanthanum hexaboride (LaB6) ligature within semi-continuous electron beam casting process of selected alloys. Two ingots with nominal compositions Ti–44Al–5Nb–2Cr–1.5Zr–0.4B–0.07La and Ti–44Al–5Nb–1Cr–1.5Zr–1B–0.17La (at.%) have been synthesized and cast along with the reference alloy Ti–44Al–5Nb–3Cr–1.5Zr. Their comparative examination suggests (i) essential microstructural phase refinement effect coupled with (ii) threefold/fourfold decrease of background content of undesirable residual oxygen impurity in both alloys containing LaB6. This advanced dual activity (i–ii) of LaB6 is explained by its complete dissolution, dissociation and following re-precipitation of effective Ti-based monoboride nucleants of orthorhombic B27 structure, those being accompanied by strong internal gettering of dissolved oxygen from the melt and from boride-inoculated solid α2-Ti3Al phase with liberated elemental lanthanum. The phase composition and structure of cast alloys; state and characterization of newly precipitated TiB boride; features of La2O3 micro/nano-dimensional precipitation and oxygen gettering mechanism are reported and discussed.