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While researchers have long sought to link amorphous structures to macroscopic properties, traditional analyses focus on geometric packing, which our study reveals to be insufficient. We demonstrate this using two Pd-based metallic glasses, $\\rm {Pd}_{40}\\rm {Cu}_{40}\\rm {P}_{20}$ and $\\rm {Pd}_{40}\\rm {Ni}_{40}\\rm {P}_{20}$, which exhibit nearly identical geometries but different secondary relaxations. Electronic structure analysis uncovers the key distinction: $\\rm {Pd}_{40}\\rm {Cu}_{40}\\rm {P}_{20}$ has weaker Cu\u2013P bonds and a less developed covalent network, enabling string-like atomic motions that drive pronounced relaxation, whereas $\\rm {Pd}_{40}\\rm {Ni}_{40}\\rm {P}_{20}$\u2019s stronger Ni\u2013P interactions create a more constrained network. These findings highlight the critical role of electronic interactions and bonding fluctuations\u2014beyond geometry\u2014in governing glass dynamics. By integrating experiments and deep-learning simulations, we bridge the gap between local bonding heterogeneity and macroscopic behavior, offering new design principles for amorphous materials that prioritize electronic structure over purely geometric order. This advances glass physics by emphasizing the need to incorporate chemical interactions into structural analyses.<\/jats:p>","DOI":"10.1093\/nsr\/nwag006","type":"journal-article","created":{"date-parts":[[2026,1,14]],"date-time":"2026-01-14T12:43:58Z","timestamp":1768394638000},"source":"Crossref","is-referenced-by-count":5,"title":["Beyond geometry orders: uncovering bonding-heterogeneity-dominated structure-relaxation coupling in glasses"],"prefix":"10.1093","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-2926-7364","authenticated-orcid":false,"given":"Liang","family":"Gao","sequence":"first","affiliation":[{"name":"Wuhan National High Magnetic Field Center and School of Physics, Huazhong University of Science and Technology , Wuhan 430074 ,","place":["China"]},{"name":"Science and Technology on Surface Physics and Chemistry Laboratory , Mianyang 621908 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