A series of Mn-substituted BaMgF4 samples have been synthesized by a hydrothermal route. X-ray diffraction study reveals that the products are monophasic in nature. Scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS) studies were carried out to investigate the morphology and stoichiometry for these compounds. X-ray photoelectron spectroscoy (XPS) and electron spin resonance (ESR) studies were done to confirm the oxidation state of dopant ion. Room temperature ferromagnetism was observed on Mn substitution at the Mg site in BaMgF4 samples. The saturation magnetization increases initially, shows a peaking effect, and then decreases with further increase in Mn concentration in BaMg1-xMnxF4 (0.0 ≥ x ≥ 0.15). However, ferroelectricity was found to decrease with an increase in Mn concentration in the series of investigated BaMg 1-xMnxF4 (0.0 ≥ x ≥ 0.15) samples. First-principle calculations, using the projector augmented wave potentials on Mn-substituted BaMgF4, confirmed the decrease in magnetic moment with an increase in Mn content beyond certain concentration. These samples exhibit very weak magnetocapacitive coupling, which can be attributed to the very small magnetic signal observed in these samples. © 2011 American Chemical Society.