Ba 0.5 Sr 0.5 Co 0.6 Fe 0.4 O 3−δ (BSCF5564) was synthesized by nitric acid aided EDTA–citric acid complexing sol-gel method (NECC). Both, the phase formation temperature and time of BSCF5564 synthesized NECC were found to be low i.e. single perovskite phase formation temperature is 200 °C less as compared to the conventional method of synthesis. The orthorhombic perovskite structure has been formed after calcination at 800 °C for 5 h. Scanning electron microscopy reveals the formation of porous material constituting nano-sized and irregularly shaped rod-like structure with particle size approximately ranges from 90 to 160 nm. The total weight loss of the BSCF5564 sample comes out to be 6.6%, indicating that quadrivalence state Co 4+ and Fe 4+ in the sample have been completely reduced to the trivalent state Co 3+ and Fe 3+ due to thermal analysis. The value of E a for BSCF5564 prepared by NECC was 0.2288 eV. The electrical conductivity of BSCF5564 synthesized by NECC is observed to be steady at high temperature (above 700 °C).