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Open mesopores expose otherwise buried junctions, shorten diffusion pathways, and create confined nanospaces, while heterointerfaces generate built\u2010in electric fields and interfacial barriers that steer carrier migration and reaction trajectories. Despite substantial advances in mesoporous materials and heterostructures, the mesopore\u2010enabled amplification of heterojunction functions has not been systematically articulated. This Review reframes MHJs through the concept of effective heterojunctions, emphasizing active interface accessibility and local electronic perturbation validity as central design criteria. The mechanistic roles of mesoporosity in interfacial barrier modulation, charge utilization, and microenvironment regulation are delineated, and their manifestations across representative MHJ configurations, synthetic strategies, and applications are systematically examined. Key challenges and opportunities are also outlined in artificial intelligence (AI)\u2010guided predictive design, effective junction quantification, operando characterization, and scalable synthesis. This Review aims to establish a clearer guiding principle to promote MHJs progression from experience\u2010based material integration toward precise interface programming.<\/jats:p>","DOI":"10.1002\/adma.75246","type":"journal-article","created":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T07:30:20Z","timestamp":1791185420000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Architecting Mesoporous Heterojunctions via Programmable Interfacial Engineering"],"prefix":"10.1002","author":[{"given":"Lingxiao","family":"Xue","sequence":"first","affiliation":[{"name":"Department of Chemistry State Key Laboratory of Coatings for Advanced Equipment Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University  Shanghai P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2793-4340","authenticated-orcid":false,"given":"Wenhe","family":"Xie","sequence":"additional","affiliation":[{"name":"Department of Chemistry State Key Laboratory of Coatings for Advanced Equipment Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University  Shanghai P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junhao","family":"Ma","sequence":"additional","affiliation":[{"name":"School of Environment and Architecture University of Shanghai for Science and Technology  Shanghai P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Limin","family":"Wu","sequence":"additional","affiliation":[{"name":"Institute of Energy and Materials Chemistry Inner Mongolia University  Hohhot P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0657-9397","authenticated-orcid":false,"given":"Yonghui","family":"Deng","sequence":"additional","affiliation":[{"name":"Department of Chemistry State Key Laboratory of Coatings for Advanced Equipment Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University  Shanghai P. R. China"},{"name":"School of Environment and Architecture University of Shanghai for Science and Technology  Shanghai P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,10,5]]},"reference":[{"key":"e_1_2_12_2_1","volume-title":"VLSI Electronics: Microstructure Science","author":"Einspruch N. 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