Magnesium is replaced systematically by zinc in Ni0.2Mg0.8‐xZnxFe2O4 (x = 0.2–0.8) prepared by microwave‐assisted solid‐state reaction route. The structure is confirmed by X‐ray diffractograms. An improvement in initial permeability is observed with substituent in Ni0.2Mg0.8‐xZnxFe2O4 due to increase in average grain size. The obtained permeability values are varying between 106 and 687 at 1 MHz. The permeability plots revealed that Curie‐transition temperature (Tc) is decreasing with increase in zinc. Both x = 0.2 and 0.4 compositions show low relative loss factor of order 10−5 to 10−4, which are exhibiting required magnetic properties for transformer and inductor core applications.