Abstract: Structures and phase transitions for the isostructural series of compounds KFeO2, RbFeO2 and CsFeO2 have been systematically studied by synchrotron X-ray high resolution powder diffraction experiments and in case of CsFeO2 also by single crystal diffractometry. At room temperature, all of the three compounds crystallize in the orthorhombic (Pbca) KGaO2 type of structure consisting of a three dimensional network of corner-sharing [FeO4/2]− tetrahedra, which at elevated temperatures shows a reversible phase transformation to a cubic structure (space group ). For KFeO2, RbFeO2 and CsFeO2 this phase transformation takes place at 1003K, 737K and 350K respectively, as confirmed by differential scanning calorimetry and X-ray diffraction. Upon heating through the transitions the major structural changes are driven by the onset or enhancement of librational motion of the FeO4 tetrahedra. Due to this phenomenon the Fe–O–Fe bonds appear to step-wise getting straight, seemingly approaching 180° within the time and space averaged structure. [Copyright &y& Elsevier]