Structural and magnetic properties of polycrystalline BiFeO3, Bi0.9Ca0.1FeO2.95, Bi0.9Ba 0.05Ca0.05 FeO2.95, and Bi0.9Ba 0.1FeO2.95 ceramic samples were studied to establish the effects of doping in BiFeO3 on the magnetic property. X-ray diffraction data of the undoped and doped BiFeO3 samples were refined to a rhombohedral structure with space group R3c. X-ray photoelectron spectroscopy study showed the formation of a single-phase in both the undoped and doped BiFeO3 ceramics with Fe in the 3 valence state. Ca doped and Ba-Ca co-doped BiFeO3 ceramic samples show weak ferromagnetic ordering at room temperature. This observation makes Ca doped and Ba-Ca co-doped BiFeO3 samples an interesting material system for magnetoelectric coupling studies. © 2012 American Institute of Physics.