In this study, Pd 75Co 25-xAu x/C ternary catalysts with varying x content are synthesized by the deposition-precipitation approach with hydrogen reduction at 390 K for the oxygen reduction reaction (ORR). The roles of Au in the modification of structures, surface species and electrochemical properties of PdCo/C catalysts are investigated. X-ray diffraction results reveal that although the low reduction temperature does not benefit the Co alloying with Pd, Pd-Au alloys are preferentially formed. Moreover, it confirms that the incorporation of Au into a Pd-Co system contributes to the generation of inhomogeneous alloy structure. Fine structural details determined by X-ray absorption spectroscopy indicate that Au addition improves the heteroatomic intermixing extent of alloy nanocatalysts, especially for Pd 75Co 10Au 15/C (Au 15) catalysts. Surface characterization by temperature programmed reduction suggests that a Pd-rich surface gradually changes to Pd, Au and alloy mixed surfaces when the Au content is larger than 15 at%. Regarding the electrochemical results, Au 15 displays the superior ORR performance among all samples due to the improved heteroatomic intermixing extent, large electrochemical surface area and multiple coexisting surface species. Furthermore, it also displays a better stability than Pd/C and Pd 75Co 25/C catalysts after accelerated durability tests.