Multiferroic BiFeO 3 ceramic powders were synthesized through high-energy ball milling. The structural, microstructural and magnetic properties of the obtained samples were carefully determined. The obtained samples were very fractured and strained due to the employed milling conditions, motivating the agglomeration of the nanopowders. The unit cell, Mössbauer and magnetic parameters presented considerable alterations in comparison with those for bulk materials, as a consequence of mechanosynthesis. The modification of BiFeO 3 with 5 mol% of Mn ions do not induces significant microstructural or structural alterations in as-milled or annealed samples. However, an intense magnetization decreasing was observed.338 233239Fiebig, M., Lottermoser, Th., Fröhlich, D., Goltsev, A.V., Pisarev, R.V., Observation of coupled magnetic and electric domains (2002) Nature, 419, pp. 818-820. , And references thereinLiu, J.-M., Li, Q.C., Gao, X.S., Yang, Y., Zhou, X.H., Chen, X.Y., Liu, Z.G., Order coupling in ferroelectromagnets as simulated by a Monte Carlo method (2002) Phys. Rev. B, 66, pp. 054416-1-054416-11. , And references thereinHill, N.A., Why Are there so few magnetic ferroelectrics? (2000) J. Phys. Chem. B, 104, pp. 6694-6709. , And references thereinUeda, K., Tabata, H., Kawai, T., Coexistence of ferroelectricity and ferromagnetism in BiFeO 3-BaTiO3 thin films at room temperature (1999) Appl. Phys. Lett., 75, pp. 555-557Kumar, M.M., Srinivas, A., Suryanarayana, S.V., Dielectric relaxation in Ba0.96Bi0.04Ti 0.96Fe0.04O3 (1998) J. Appl. Phys., 84, pp. 6811-6814Kumar, M.M., Srinivas, A., Suryanarayana, S.V., Electrical and dielectric properties in double doped BaTiO3 showing relaxor behaviour (1999) J. Appl. Phys., 86, pp. 1634-1637De Sitter, J., Dauwe, C., De Grave, E., Govaert, A., Robbrecht, G., On the magnetic properties of the basic compounds in the Fe 2O3-Bi2O3 system (1977) Physica B, 86-88, pp. 919-920Wang, Y.P., Zhou, L., Zhang, M.F., Chen, X.Y., Liu, J.-M., Liu, Z.G., Room-temperature saturated ferroelectric polarization in BiFeO 3 ceramics synthesized by rapid liquid phase sintering (2004) Appl. Phys. Lett., 84, pp. 1731-1733Pradhan, A.K., Zhang, K., Hunter, D., Dadson, J.B., Loutts, G.B., Bhattacharya, P., Katiyar, R., Burger, A., Magnetic and electrical properties of single-phase multiferroic BiFeO3 (2005) J. Appl. Phys., 97, pp. 093903-1-093903-4Yang, C.-H., Koo, T.Y., Jeong, Y.H., How to obtain magnetocapacitance effects at room temperature: The case of Mn-doped BiFeO3 (2005) Sol. State Comm., 134, pp. 299-301Ederer, C., Spaldin, N.A., A new route to magnetic ferroelectrics (2004) Nature Mat., 3, pp. 849-851. , And reference thereinDijjkamp, D., Vankatesan, T., Wu, X.D., Saheen, S.A., Jisrawi, N., Min-Lee, Y.H., McLean, W.L., Croft, M., Preparation of Y-Ba-Cu oxide superconductor thin films using pulsed laser evaporation from high Tc bulk material (1987) Appl. Phys. Lett., 51, pp. 619-621. , And references thereinScholz, G., Stösser, R., Klein, J., Silly, G., Buzaré, J.Y., Lagigant, Y., Ziemer, B., Local structural orders in nanostructured Al2O3 prepared by high-energy ball milling (2001) J. Phys. Cond. Matter, 14, pp. 2101-2117Calka, A., Wexler, D., Mechanical milling assisted by electrical discharge (2002) Nature, 419, pp. 147-151Cótica, L.F., Zanatta, S.C., Rocha, M.A., Santos, I.A., Paesano Jr., A., Da Cunha, J.B.M., Hallouche, B., Phase evolution and magnetic properties of high-energy ball-milled hematite-alumina system (2004) J. Appl. Phys., 95, pp. 1307-1314. , And references thereinSosnovska, I., Przenioslo, R., Fischer, P., Murashov, V.A., Neutron diffraction of the crystal and magnetic structures of BiFeO 3 and Bi0.97la0.07FeO3 (1996) J. Mag. Mag. Mat., 160, pp. 384-385De Sitter, J., Dauwe, C., De Grave, E., Govaert, A., On the Mössbauer parameters in BiFeO3 (1976) Solid State Comm., 18, pp. 645-646