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This view is incomplete. While 4f multiplet energies are largely atomic in origin, their radiative probabilities, energy\u2010transfer kinetics, and quenching pathways are fundamentally governed by the host lattice. Crystal symmetry and structural phase determine dopant coordination, crystal\u2010field asymmetry, interionic spacing, and migration topology, thereby reprogramming emission intensity and dynamics without altering chemical composition. In this Review, we argue that structural engineering constitutes an independent and underexploited design axis in rare\u2010earth photonics. We examine how symmetry breaking modulates parity mixing, how lattice packing reorganizes multipolar coupling, and how phase boundaries generate emergent energy\u2010transfer pathways inaccessible in single\u2010phase crystals. We further discuss nanoscale kinetics that enable access to metastable polymorphs and field\u2010induced structural transformations driven by pressure and irradiation. By reframing rare\u2010earth luminescence as a structure\u2010programmed phenomenon rather than a dopant\u2010limited one, we outline opportunities and unresolved challenges in the predictive design of structure\u2010engineered RE nanomaterials.<\/jats:p>","DOI":"10.1002\/adma.73890","type":"journal-article","created":{"date-parts":[[2026,7,6]],"date-time":"2026-07-06T07:03:37Z","timestamp":1783321417000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Structural Engineering of Rare\u2010Earth Nanomaterials"],"prefix":"10.1002","author":[{"given":"Peng","family":"Pei","sequence":"first","affiliation":[{"name":"Department of Surgery Yong Loo Lin School of Medicine National University of Singapore  Singapore Singapore"},{"name":"Department of Chemistry National University of Singapore  Singapore Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chang","family":"Gu","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuyang","family":"Gu","sequence":"additional","affiliation":[{"name":"Department of Chemistry National University of Singapore  Singapore Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9236-9160","authenticated-orcid":false,"given":"Zichao","family":"Luo","sequence":"additional","affiliation":[{"name":"Eye Institute and Department of Ophthalmology Eye &amp; ENT Hospital Fudan University NHC Key Laboratory of Myopia and Related Eye Diseases Key Laboratory of Myopia and Related Eye Diseases Chinese Academy of Medical Sciences  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8569-7721","authenticated-orcid":false,"given":"Xian","family":"Qin","sequence":"additional","affiliation":[{"name":"Strait Institute of Flexible Electronics (SIFE Future Technologies) Fujian Key Laboratory of Flexible Electronics Fujian Normal University  Fuzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2517-5790","authenticated-orcid":false,"given":"Xiaogang","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Surgery Yong Loo Lin School of Medicine National University of Singapore  Singapore Singapore"},{"name":"Department of Chemistry National University of Singapore  Singapore Singapore"},{"name":"The N.1 Institute for Health National University of Singapore  Singapore Singapore"},{"name":"Institute for Health Innovation &amp; Technology National University of Singapore  Singapore Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,7,6]]},"reference":[{"key":"e_1_2_12_2_1","doi-asserted-by":"crossref","first-page":"924","DOI":"10.1038\/nnano.2015.251","article-title":"Controlling Upconversion Nanocrystals for Emerging Applications","volume":"10","author":"Zhou B.","year":"2015","journal-title":"Nature Nanotechnology"},{"key":"e_1_2_12_3_1","doi-asserted-by":"crossref","first-page":"5519","DOI":"10.1021\/acs.chemrev.1c00644","article-title":"Rare\u2010Earth Doping in Nanostructured Inorganic Materials","volume":"122","author":"Zheng B.","year":"2022","journal-title":"Chemical Reviews"},{"key":"e_1_2_12_4_1","doi-asserted-by":"crossref","DOI":"10.1002\/adom.201801417","article-title":"A New Generation of NIR\u2010II Probes: Lanthanide\u2010Based Nanocrystals for Bioimaging and Biosensing","volume":"7","author":"Fan Y.","year":"2019","journal-title":"Advanced Optical Materials"},{"key":"e_1_2_12_5_1","article-title":"Progress and Prospects of Persistent Luminescent Nanocrystals in Biomedical Applications","volume":"14","author":"Pei P.","year":"2026","journal-title":"Advanced Optical Materials"},{"key":"e_1_2_12_6_1","volume-title":"Micro\u2010ISV: From Vision to Reality","author":"Walsh B.","year":"2006"},{"key":"e_1_2_12_7_1","doi-asserted-by":"crossref","first-page":"1128","DOI":"10.1002\/anie.201208218","article-title":"Breakdown of Crystallographic Site Symmetry in Lanthanide\u2010Doped NaYF4 Crystals","volume":"52","author":"Tu D.","year":"2013","journal-title":"Angewandte Chemie International Edition"},{"key":"e_1_2_12_8_1","doi-asserted-by":"crossref","first-page":"750","DOI":"10.1103\/PhysRev.127.750","article-title":"Optical Absorption Intensities of Rare\u2010Earth Ions","volume":"127","author":"Judd B. 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