Fe doping effect on the local magnetic property of La0.7Ca0.3Mn1−xFexO3 (0.4 ≤ x ≤ 0.55) was investigated by means of 57Fe Mössbauer spectroscopy. The X-ray diffraction patterns and the isomer shifts of the 57Fe Mössbauer spectra demonstrate that all the Fe ions are high-spin trivalent and share the B site lattice positions with Mn ions. The sample of La0.7Ca0.3Mn0.6Fe0.4O3 (x = 0.4) was found to be in the paramagnetic state even at 8 K. For the samples with high Fe contents, however, magnetic sextet(s) arising from local magnetic ordering were observed in the low-temperature spectrum of La0.7Ca0.3Mn0.5Fe0.5O3 (x = 0.5), and also in all the spectra of La0.7Ca0.3Mn0.45Fe0.55O3 (x = 0.55) measured in the range of 8 K—room temperature. These observations suggest that randomly distributed Fe3+ ions interfere with the double exchange interaction in Mn3+–O–Mn4+, and antiferromagnetic ordering arises from superexchange interaction in Fe3+–O–Fe3+ at high Fe content. [ABSTRACT FROM AUTHOR]