Ytterbium (Yb) substituted magnesium ferrite materials (MgYbxFe2−xO4 with x = 0.00, 0.025, 0.050, 0.075, 0.10) have been prepared by the Sol–gel method. XRD analysis revealed that the prepared samples are cubic spinel with single phase till the content ‘x’ equals 0.05. At higher content x ≥ 0.075, Yb substituted samples possessed YbFeO3 phase along with the cubic spinel phase. A significant decrease of ~34.7 nm in crystallite size is noted in response to the increase in Yb substitution level. The room temperature dc resistivity increases gradually from 3.47 × 107 to 2.63 × 108 Ω-cm as the substitution of Yb is increased. Temperature dependent DC electrical resistivity of all the samples exhibits semiconducting behavior. Yb substituted materials can be suitable to limit the eddy current losses for microwave applications. VSM indicated the existence of an appreciable fraction of ferrimagnetic properties at room temperature. The saturation magnetization of the samples decreases from 60 to 33 emu/g. Saturation magnetization and remanence decreased while coercivity increased with Yb substitution.