La0.6Sr0.4Co0.2Fe0.8O3 (LSCF)−La0.8Sr0.2MnO3 (LSM) heterostructure crystalline materials have been synthesized in a simple, one-step via reaction-deposition process using a molten salt. Two-phase perovskite composites can be synthesized in times as short as 10 minutes in a molten salt solvent. X-ray diffraction and S/TEM energy dispersive X-ray spectroscopy have been utilized to confirm the formation of an LSM shell on LSCF cores in all samples when adjusting dwell time, core size, weight ratio between core and shell precursors, and weight ratio of powder to salt. Specifically, decreasing the LSCF core size increases core−shell yield. Smaller cores result in a greater density of facets on the crystal surface and provide more favorable sites for LSM heterogeneous nucleation. By decreasing the weight ratio of shell precursor to core decreases shell thickness, and reduces the number of homogeneously nucleated LSM nanoparticles, and thereby increases core−shell yield. Increasing the amount of molten salt solvent relative to precursors decreases supersaturation in the melt and results in less uniform, and isolated shell deposition on the cores. The synthesized heterostructred nanoparticles have been functionalized into electrodes for solid oxide fuel cells and electrolysis cells. Symmetrical cells fabricated from baseline LSCF electrodes are compared with symmetrical cells fabricated from the molten salt-synthesized heterostructred electrodes. The heterostructured electrodes are shown to have significantly lower polarization resistance compared to baseline LSCF electrodes, showing the promise of the molten salt process to achieve heterostructured electrodes with substantially reduced polarization resistance.