Polycrystalline Er2−xCexFe14B (x=0.25, 0.5, 1.0) compounds have been studied by 57Fe Mössbauer spectroscopy and by differential scanning calorimetry (DSC) in the temperature range 80–470K. The spin reorientation phenomenon has been studied extensively by narrow step temperature scanning in the vicinity of the spin reorientation temperature. It was found that in the region of transition, each Mössbauer subspectrum splits into two Zeeman sextets, which are characterised by different hyperfine magnetic fields and quadrupole splittings. A consistent way of describing the Mössbauer spectra in the reorientation region, below and above, was proposed. The composition and temperature dependencies of hyperfine interaction parameters and subspectra contributions were derived from experimental spectra.The endothermic DSC peaks were observed for all studied compounds, which correspond to the transition from basal plane to axial easy magnetisation direction on increasing the temperature. The spin reorientation temperatures and the enthalpies of transitions were established from DSC data. The spin arrangement diagram was constructed and the spin reorientation temperatures obtained by the two methods were compared.