Samples in the system Bi1−xYbxFeO3 (0.02 ≤ × ≤ 0.07) have for the first time been prepared by mechanical activation followed by sintering. XRD and DSC measurements show that the solubility limit of ytterbium in the R3c Bi1−xYbxFeO3 system is reached at x∼0.03. Higher ytterbium contents lead to a two-phase mixture of a main R3c phase of approximate composition Bi0.97Yb0.03FeO3 and ytterbium enriched secondary phases that cannot be readily indexed or quantified due to their small amount. DSC and temperature-dependent XRD showed that while the magnetic ordering temperature, TN, was unaffected by Yb substitution, the ferroelectric ordering, TC, declined. Temperature-dependent XRD patterns show that all samples exhibit rhombohedral R3c to orthorrhombic Pnma phase transitions. Diffuse reflectance spectroscopy suggests the potential use of the samples in photocatalytic applications due to their low band gap energy. Impedance spectroscopy and magnetic measurements show that samples are electrically homogenous and highly insulating, exhibiting antiferromagnetic behaviour at room temperature ; Peer reviewed