•PCO–GDC composites are studied as a cathode for SOFCs.•The rate-determined step of the overall electrode process vs. temperature was defined.•PCO–GDC33 composite gave the lowest area surface resistance of 0.41Ωcm2 at 700°C.•PCO–GDC33 is preferred to use as a cathode material for IT-SOFCs. Pr2CuO4–Ce0.9Gd0.1O1.95 (PCO–GDC) composites screen printed on Ce0.9Gd0.1O1.95 (GDC) electrolyte were considered as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). Phase composition, microstructure and electrochemical properties were investigated by X-ray powder diffraction (XRD), scanning electron microscopy and AC impedance spectroscopy, respectively. The oxygen reduction on porous PCO–GDC electrode applied on CGO electrolyte was studied in a symmetrical cell configuration by AC impedance spectroscopy at OCV conditions at 670–730°C and pO2=10-2-0.21atm. The charge transfer process and the dissociation of adsorbed molecular oxygen were found to be rate-determining steps of the oxygen reduction reaction. Results reveal that both GDC addition and electrode morphology have strong influence on area specific resistance (ASR) of the electrode/electrolyte interface. The lowest ASR value of 0.41Ωcm2 was achieved for the composition containing 33wt.% GDC at 700°С in air. The data obtained allow to consider the PCO–GDC33 composite as a promising cathode material for IT-SOFCs.