The efficiency of oxygen reduction reaction (ORR) in the proton-exchange membrane fuel cells (PEMFCs) heavily relies on the surface Pt atom arrangement, which can be represented by the Pt-Pt average distance. Here, we employed density functional theory (DFT) to examine the influence of Pt arrangement on the ORR efficiency of Cu@Pd core-shell and high-entropy alloy catalysts. Our DFT calculations reveal that a shorter Pt-Pt average distance on the surface leads to a lower O2 dissociation barrier. Nevertheless, a shorter Pt-Pt average distance is not thermodynamically favored for the Cu@Pt catalyst. Moreover, we discovered a robust correlation between the level of the d-band center of the catalyst and the O2 adsorption energy. To explore the potential of controlling Pt arrangement, we investigated the use of NbMoTaW high-entropy alloy (HEA) substrates. Our findings suggest that HEA substrates provide promising surface chemistry for tuning Pt arrangement and controlling the O2 dissociation barrier.