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In this context, the growth of hBN on liquid metal catalysts is promising, as the atomically flat liquid surfaces are assumed to promote high\u2010quality 2D growth, an expectation largely informed by graphene. Here, we implement an involved operando methodology to monitor and quantify hBN growth on molten copper (Liq\u2010Cu) and re\u2010solidified single\u2010crystal copper (SC\u2010Cu) under near\u2010ambient\u2010pressure conditions, enabling real\u2010time identification of growth stages, morphology, and interfacial structure. Contrary to expectation, Liq\u2010Cu promotes multilayer and three\u2010dimensional domain formation, whereas SC\u2010Cu predominantly yields monolayer\u2010limited growth. This substrate\u2010phase dependence correlates with a larger adsorption height of hBN on Liq\u2010Cu than on SC\u2010Cu, as determined by X\u2010ray reflectivity and supported by machine\u2010learning\u2010accelerated molecular dynamics simulations. Direct comparison with graphene on Cu further reveals a distinct directional bonding character at the hBN\/Cu interface, which rationalizes the observed adsorption\u2010height trends. More generally, these trends across 2D materials and substrates identify the resulting interfacial stabilization, together with macroscopic factors such as precursor solubility, as a complementary design parameter governing mono\u2010 vs. multilayer growth in 2D material\u00a0synthesis.<\/jats:p>","DOI":"10.1002\/advs.76354","type":"journal-article","created":{"date-parts":[[2026,7,20]],"date-time":"2026-07-20T12:46:02Z","timestamp":1784551562000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Hexagonal Boron Nitride on Liquid and Single\u2010Crystal Copper: Operando X\u2010Ray and Atomistic Insights into Growth and Interfacial Structure"],"prefix":"10.1002","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0009-0007-2246-2387","authenticated-orcid":false,"given":"Nikoo","family":"Ghanadan","sequence":"first","affiliation":[{"name":"The European Synchrotron Radiation Facility (ESRF) Grenoble 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