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This difficulty arises because interfacial energetics and chain\u2010stretching penalties are inherently coupled in conventional linear architectures, where interfacial area and chain conformation cannot be tuned independently. To address this limitation, we synthesized a systematic library of polyethylene oxide (PEO)\u2013 and polydimethylsiloxane (PDMS)\u2013grafted bottlebrush random copolymers (BRCPs) via ring\u2010opening metathesis polymerization, in which the backbone degree of polymerization and side\u2010chain asymmetry were independently varied to program molecular architecture. Small\u2010angle and wide\u2010angle x\u2010ray scattering revealed that longer PDMS side chains suppressed the crystallization of shorter PEO chains and drove a systematic increase in lamellar spacing. Confinement imposed by the bottlebrush backbone further promoted the formation of highly asymmetric lamellar morphologies even at pronounced compositional asymmetries. Motivated by these results in the solid state, we additionally examined the fluid\u2013fluid interfacial behavior of these BRCPs, finding that side\u2010chain length governs interfacial tension and that architectural asymmetry and chain mobility enable spontaneous emulsification through Marangoni\u2010driven instabilities. Overall, these findings contribute molecular\u2010level design rules governing crystallization and lamellar organization in the solid state, as well as principles for engineering tailored emulsifiers and dynamic interfacial materials.<\/jats:p>","DOI":"10.1002\/anie.2377439","type":"journal-article","created":{"date-parts":[[2026,3,27]],"date-time":"2026-03-27T14:18:29Z","timestamp":1774621109000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Synthesis of Asymmetric Bottlebrush Random Copolymers and Their Assembly in the Bulk and at Fluid Interfaces"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7163-4479","authenticated-orcid":false,"given":"Kyoungwon","family":"Lee","sequence":"first","affiliation":[{"name":"Department of Polymer Science and Engineering University of Massachusetts  Amherst Massachusetts 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