The electronic structure and magnetic properties of polycrystalline BaTi1-xMnxO3 (x ¼ 0e0.1) compounds prepared by solid-state reactions were studied. The results revealed that the increase in Mn content (x) did not change the oxidation numbers of Ba (þ2) and Ti (þ4) in BaTi1-xMnxO3. However, there is the change in Mn valence that Mn3þ,4þ ions coexist in the samples with x ¼ 0.01e0.04 while Mn4þ ions are almost dominant in the samples with x ¼ 0.06e0.1. We also point out that Mn3þ and Mn4þ ions substitute for Ti4þ and prefer locating in the tetragonal and hexagonal BaTiO3 structures, respectively, in which the hexagonal phase constitutes soon as x ¼ 0.01. Particularly, all the samples exhibit roomtemperature ferromagnetism. Ferromagnetic order increases with increasing x from 0 to 0.02, but decreases as x 0.04. We think that ferromagnetism in BaTi1-xMnxO3 is related to lattice defects and/or exchange interactions between Mn3þ and Mn4þ ions.