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Cell\u2010mimicking complex hollow architectures with precise active components distributions are particularly important, while their synthesis remains highly challenging. Herein, a \u201ctop\u2010down\u201d chemical surgery strategy is introduced to engrave the 3\u2010aminophenol formaldehyde resin (APF) spheres at nanoscale. Undergoing the cleavage of (Ar)C\uf8ffN bonds with ethanol as chemical scissors and subsequent repolymerization process, the Solid APF transform to multilevel hollow architecture with precise nanospatial distribution of organic functional groups (e.g., hydroxymethyl and amine). The transformation is tracked by electron microscopy and solid\u2010state <jats:styled-content>nuclear magnetic resonance<\/jats:styled-content>\u00a0techniques, the category and dosage of alcohol are pivotal for constructing\u00a0multilevel hollow structures. Moreover, it is demonstrated the evolution of nanostructures accompanied with unique organic microenvironments is able to accurately confine multiple gold (Au) nanoparticles, leading to the formation of pomegranate\u2010like particles. Through selectively depositing <jats:styled-content>palladium (<\/jats:styled-content>Pd) nanoparticles onto the outer shell, bimetallic Au@APF@Pd catalysts are formed, which exhibit excellent hydrogenation performance with turnover frequency (TOF) value up to 11257\u00a0h<jats:sup>\u20131<\/jats:sup>. This work provides an effective method for precisely manipulating the nanostructure and composition of polymers at nanoscale and sheds light on the design of catalysts with precise spatial active components.<\/jats:p>","DOI":"10.1002\/adma.202205153","type":"journal-article","created":{"date-parts":[[2022,8,23]],"date-time":"2022-08-23T22:28:40Z","timestamp":1661293720000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":44,"title":["Multilevel Hollow Phenolic Resin Nanoreactors with Precise Metal Nanoparticles Spatial Location toward Promising Heterogeneous Hydrogenations"],"prefix":"10.1002","volume":"34","author":[{"given":"Yutong","family":"Pi","sequence":"first","affiliation":[{"name":"State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences  457 Zhongshan Road Dalian 116023 China"},{"name":"University of Chinese Academy of Sciences  19A Yuquan Rd, Shijingshan District Beijing 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