Various phases of the titantium rich part of the Ti‐Fe binary system were obtained by thermal treatments and were identified by Mo¨ssbauer spectroscopy and x‐ray diffraction. Room‐temperature Mo¨ssbauer parameters were derived for the following phases: &agr;m, &agr;, &Vthgr;, &ohgr;, &bgr;, and TiFe. The range of concentrations for which an athermal &ohgr; phase appears upon quenching was found to be 2.7⩽CFe⩽5 wt%. The athermal &ohgr; phase disappears during aging at 285 °C for 15 h, when the alloy containsCFe⩽4.0 wt%. Martensite &agr;mwas found to form when Fe concentrations were ⩽2.7 wt.%. After quenching from the &bgr; field, the &bgr; phase retains when the Fe content of the alloy is ⩾2.7 wt.%. The &Vthgr; phase forms during aging at temperatures above 280 °C, for alloys with a Fe content ⩽2.7 wt.%. Room‐temperature Mo¨ssbauer parameters are given to enable phases to be indentified and analyzed by means of Mo¨ssbauer spectroscopy.