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Manganese containing La–Fe–Si alloys are important magnetocaloric compounds, since Mn atoms prevent segregation of hydrogen in partially hydrogenated La–Fe–Mn–Si alloys when their Curie temperature is tuned to room temperature by hydrogen. The effect of Mn alloying on the Fe atomic magnetic moment μFe is still rather unexplored. Therefore, we investigated the (local) magnetic and electric hyperfine interactions in the strongly magnetocaloric compound LaFe11.3Mn0.3Si1.4 and, for comparison, LaFe11.6Si1.4 by 57Fe Mössbauer spectroscopy, and the global magnetic properties by vibrating sample magnetometry. The NaZn13 structure was confirmed by x-ray diffraction. Two non-equivalent Fe lattice sites are known to exist in this material: the (96i) sites (FeII) of low local symmetry, and the highly symmetrical (8b) sites (FeI). At room temperature in the paramagnetic state, the electric hyperfine parameters of Fe atoms on both sites were obtained. At low temperatures (4.8 K), the observed magnetically split nuclear Zeeman sextets with broad apparent lines were analyzed in terms of a distribution P(Bhf) of hyperfine magnetic fields Bhf. The average hyperfine field 〈Bhf〉, originating predominantly from FeII sites, was found to be rather high (30.7(1) T at 4.8 K) for LaFe11.6Si1.4, and the approximate relation 〈Bhf〉 = AμFe is confirmed for FeII sites, with A = 14.2 T/μB. 〈Bhf〉 is significantly reduced (to 27.7(1) T at 4.8 K) for the Mn-containing sample LaFe11.3Mn0.3Si1.4, providing evidence for a reduction by 9.7% of the average Fe atomic moment μFe from ~2.16 μB to a value of ~1.95 μB by Mn substitution of Fe. Our Mössbauer results are in good agreement with magnetometry, which reveals a reduction of the saturation magnetization of Ms = 163.1(1) Am2 kg−1 of LaFe11.6Si1.4 by 10.5% due to Mn substitution. [ABSTRACT FROM AUTHOR]