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Deformation microstructure of orthorhombic-α\" martensite in a Ti-7.5Mo (wt.%) alloy was investigated by tracking a local area of microstructure using scanning electron microscopy, electron back-scattered diffraction, and transmission electron microscopy. The as-quenched α\" plates contain {111} α\" -type I transformation twins generated to accommodate transformation strain from bcc-β to orthorhombic-α\" martensite. Tensile deformation up to strain level of 5% induces {112} α\" -type I deformation twins. The activation of {112} α\" -type I deformation twinning mode is reported for the first time in α\" martensite in β-Ti alloys. {112} α\" -type I twinning mode was analyzed by the crystallographic twinning theory by Bilby and Crocker and the most possible mechanism of atomic displacements (shears and shuffles) controlling the newly reported {112} α\" -type I twinning were proposed.