[en] Highlights: •γ-BIMNVOX was synthesized by ethylene glycol–citrate sol–gel route. •γ-BIMNVOX crystallizes by 25-min microwave-assisted calcination. •Smaller particle sizes for microwave calcined BIMNVOX samples. •Best oxide-ion performance for microwave calcined BIMNVOX samples. -- Abstract: Samples of γ-BIMNVOX (Bi₂V_1−xMn_xO_5.5−x/2; 0.13 ⩽ x ⩽ 0.20) system were synthesized by an ethylene glycol–citrate sol–gel route. The resulting xerogels were then calcined by the microwave heating using a modified domestic microwave oven operated at 2.45 GHz. Microwave-assisted calcination samples in comparison with other conventionally calcined samples were characterized in terms of phase crystallization, stabilization and particle size using simultaneous thermogravimetric–differential thermal analysis (TG–DTA), X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM). The AC impedance spectroscopy was employed for electrical characterization. It was found that the microwave-assisted calcination route successfully produces better crystalline stabilized γ-BIMNVOX samples with appreciably small average particle sizes after only 25 min of microwave heating. The electrical properties of microwave calcined γ-BIMNVOX system make it an advanced low-temperature solid electrolyte suitable for use in oxide-ion based electrochemical applications