The orientation relationships among TiB (B27), B2, and Ti 3 Al phases have been investigated by transmission electron microscopy. By using the composite selected-area electron diffraction technique, the orientation relationship between TiB (B27) and B2 was determined to be [100] TiB jj[001] B2 , (001) TiB jj(010) B2 ; and that between TiB (B27) and Ti 3 Al was ½010 TiB jj½1120 Ti 3 Al , ð001Þ TiB jjð0001Þ Ti 3 Al . These orientation relationships have been predicted precisely by the method of coincidence of reciprocal lattice points.