Xinyi Shen, Xue Zhang, Wei Hu, Xiaolin Tai, Wenzhi Li, Yuwen Chen, Mengzhao Zhu, Xu Zhang, Qinghua Zhang, Lin Gu, Yue Lin, Yuen Wu, Mei Sun, Li‐Ming Yang, Xiaokang Liu, Linlin Cao, Tao Yao
ABSTRACT Understanding and controlling atomic‐level interactions within multicomponent alloys provides a promising avenue to drive multistep tandem catalysis. Herein, we develop an atomic symmetry‐breaking PtFeCoCu multicomponent alloy that disrupts long‐range order and local coordination homogeneity and identify the nature of its enhanced performance for oxygen reduction reaction (ORR). The deliberate symmetry breaking, featured by heterogeneous local coordination and anisotropic strain, enriches the Pt environment with additional transition‐metal neighbors. These distortions activate multicomponent interactions and tune the Pt electronic structure, promoting ORR intermediate conversion while suppressing component dissolution. Consequently, PtFeCoCu reaches a half‐wave potential of 0.95 V RHE and a mass activity of 3.53 A mg Pt −1 at 0.9 V RHE in ORR. In an H 2 ‐O 2 fuel cell, it delivers a high mass activity of 1.63 A mg Pt −1 at 0.9 V iR‐free , retaining 87.7% of its initial mass activity after 30,000 cycles. Our findings highlight symmetry breaking as a key driver with broad implications across multicomponent alloys.