LaFe1-xMnxO3 (0≤x≤0.9) samples were synthesized through the sol-gel method. According to X-ray diffraction (XRD) results, with the increase of Mn doping, the crystal structure of the sample changes from orthogonal Pnma structure to rhombohedral R3c structure, and a two-phase coexistence phenomenon exists within the range of 0.4≤x≤0.7. Using Mössbauer spectroscopy, the coexistence range of the two phases and the iron content in each phase were identified. At x=0.4, the Pnma phase contribution (91.1%) dominates, with only a slight R3c phase ...