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• Bi 1- x Yb x FeO 3 system were obtained by the solid-state method. • The compounds crystallize in the rhombohedral phase with space group R3c (1 6 1). • For the sample with x = 0.02, the transition from paramagnetic to antiferromagnetic state is observed at a Néel temperature of ∼120 K. • The insulating nature of the samples was confirmed through DC resistivity measurements. • Unsaturated hysteresis loops in electric polarization were observed, with a notable impact from leakage currents. This work reports the effect of Yb3+ substitution on the structural, magnetic, and electrical properties of the Bi 1- x Yb x FeO 3 system (x = 0.00, 0.02, 0.04, 0.05 and 0.06) synthesized via the solid-state reaction method. Structural properties at room temperature were studied by means of XRD diffraction. The XRD pattern were analyzed using Rietveld refinement. The results showed that the Bi 1- x Yb x FeO 3 samples mainly crystallize in rhombohedral phase with space group R3c (1 6 1). Magnetic measurements as a function of temperature showed two magnetic behaviors, the first for x < 0.05 and the second one for x < 0.06. From the DC resistivity measurements, the insulating nature of the samples was verified. The electrical behavior of the compounds was also investigated by means of complex impedance spectroscopy. Strong dependence of the electrical properties on the frequency and composition was observed. The electric polarization showed unsaturated hysteresis loops, strongly affected by leakage current. [ABSTRACT FROM AUTHOR]