Emission 57Fe Mössbauer spectroscopy (eMS), following the implantation of radioactive 57Mn+ ions, has been used to study the temperature dependence of the hyperfine magnetic field at Fe sites in Ba-doped BiFeO3 (BFO) thin films. 57Mn β decays (t1/2 = 90 s) to the 14.4 keV Mössbauer state of 57Fe, thus allowing online eMS measurements at a selection of sample temperatures during Mn implantation. The eMS measurements were performed on two thin film BFO samples, 88 nm and 300 nm thick, and doped to 15% with Ba ions. The samples were prepared by pulsed laser deposition on SrTiO3 substrates. X-ray diffraction analyses of the samples showed that the films grew in a tetragonal distorted structure. The Mössbauer spectra of the two films, measured at absorber temperatures in the range 301 K–700 K, comprised a central pair of paramagnetic doublets and a magnetic sextet feature in the wings. The magnetic component was resolved into (i) a component attributed to hyperfine interactions at Fe3+ ions located in octahedral sites (Bhf); and (ii) to Fe3+ ions in implantation induced lattice defects, which were characterized by a distribution of the magnetic field BDistr. The hyperfine magnetic field at the Fe probes in the octahedral site has a room temperature value of Bhf = 44.5(9) T. At higher sample temperatures, the Bhf becomes much weaker, with the Fe3+ hyperfine magnetic contribution disappearing above 700 K. Simultaneous analysis of the Ba–BFO eMS spectra shows that the variation of the hyperfine field with temperature follows the Brillouin curve for S = 5/2.