The materials studied were polycrystalline compounds Er2−xTbxFe14B (x = 0.1, 0.2, 0.3, 0.4) which crystallize in a tetragonal lattice and display a variety of spin arrangements. The compounds have been measured with 57Fe Mössbauer spectroscopy over the temperature range 80–320 K in order to investigate the spin reorientation processes. Each compound was studied in a wide temperature range, with precise Mössbauer scanning in the vicinity of the transition. The set of spectra obtained for a given compound was analyzed using simultaneous fitting procedure to investigate the influence of the transition on the shape of the spectra. The fitting program was specified to analyze the transition according to the ‘two state model’: spins flip abruptly from initial angle to final arrangement (90° angle). Obtained results suggest that spin reorientation process cannot be described using only the mentioned above model. Additional computer simulations based on the Yamada–Kato model were conducted to determine temperature range and the type of spin alignments in the vicinity of the transition. These theoretical results supported by spectra analysis suggest the existence of intermediate (canted) spin arrangements in the studied compounds. The spin arrangement diagram was constructed.