Structural and magnetic characteristics of La0.7Sr0.3Mn0.957Fe0.05Zn0.05O3+γ and La0.7Sr0.3Mn0.957Fe0.05Mg0.05O3+γ manganites, in which the iron is Mossbauer isotope 57Fe, are investigated and compared. Ceramic samples were sintered in air at 1473 K. They were then exposed to heat treatments at 1223 K and various partial pressure of oxygen in the gas phase, which ensured the production of manganites with following values of non-stoichiometry index: γ = −0.005; 0.000; 0.007; 0.008 for Zn-containing manganites (ZnM), and γ = −0.022; 0.000; 0.002; 0.005 for Mg-containing manganites (MgM). All synthesized manganites have rhombohedral crystal structure. Mössbauer spectroscopy data correspond to Fe3+ (3d5) ions. Curie point and magnetization depend on γ nonmonotonically. ZnM have essentially higher values of magnetic parameters and narrowest temperature interval of “ferromagnetic-paramagnetic” transition as compared to MgM. Their structure is considered as more homogeneous, which corresponds to lower value of quadrupole splitting of Mössbauer spectra. The results obtained indicate that different effect of Zn2+ and Mg2+ ions on electromagnetic characteristics of manganites is mainly determined by the configuration of their electron shells (3d10 and 2p6, correspondingly).