Intermediate temperature solid oxide fuel cells oxygen electrodes are modified by active interfacial layers. Spray pyrolysis is used to produce thin (≈500 nm) layers of mixed ionic and electronic conductors: Sm0.5Sr0.5CoO3−δ (SSC), La0.6Sr0.4CoO3−δ (LSC), La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF), and Pr6O11 (PrOx) on the electrode–electrolyte interface. The influence of the annealing temperature on the electrode polarization (area specific resistance—ASRpol) is investigated by impedance spectroscopy of symmetrical electrodes in the temperature range of 400–700 °C. The results show that the introduction of nanocrystalline interlayers promotes an oxygen reduction reaction by extending the active surface area and improved contact between the electrode and the electrolyte. Introducing LSCF, LSC, or SSC interlayer reduces ASRpol by a factor of 4 and PrOx by a factor of 2 against the reference, powder processed LSCF electrode. At 600 °C, the obtained ASRpol values for PrOx, LSCF, LSC, and SSC interlayer are 245, 137, 119, and 107 mΩ cm2, which can be considered very low in comparison to standard powder processed oxygen electrodes. Anode supported single cell with developed LSC/LSCF electrode reveals ≈1.2 W cm−2 power output at 600 °C and maintains stable cell voltage of 0.75 V under 1 A cm−2 during 60 h of the test.