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This review establishes a unified framework for understanding these interactions across plasmonic picocavities, molecular systems, and van der Waals (vdW) materials and heterostructures. We examine key mechanisms governing extreme optical confinement, including nonlocality, electron tunneling, charge\u2013transfer effects, excitonic interactions, and phonon\/plasmon polaritons. Experimental approaches, including scanning tunneling microscopy\u2010based optical measurements, tip\u2010enhanced Raman spectroscopy, near\u2010field optical microscopy, and ultrafast spectroscopy, are discussed together with electromagnetic and quantum\u2010mechanical modeling methods. Particular emphasis is placed on how atomic\u2010scale structural variations, interfacial geometry, and material composition regulate optical response and enable applications in single\u2010molecule spectroscopy, chemical sensing, cavity\u2010modified chemistry, and quantum photonics. We further compare metallic picocavities with vdW polaritonic and hybrid plasmonic\u2013vdW platforms in terms of confinement, losses, tunability, reproducibility, and scalability. Finally, key challenges involving experimental artifacts, heating, fabrication, and quantitative metrology are critically assessed, providing perspectives toward reproducible and programmable picoscale light\u2013matter interactions.<\/jats:p>","DOI":"10.1002\/tcr.70260","type":"journal-article","created":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T05:48:02Z","timestamp":1791438482000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Picoscale Light\u2013Matter Interactions in Plasmonic, Polaritonic, and van der Waals Nanostructures"],"prefix":"10.1002","author":[{"given":"Saba","family":"Ali","sequence":"first","affiliation":[{"name":"National Center of Excellence in Analytical Chemistry University of Sindh  Jamshoro Pakistan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mustafa","family":"Tuzen","sequence":"additional","affiliation":[{"name":"Department of Chemistry Faculty of Science and Art Tokat Gaziosmanpasa University  Tokat Turkey"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9424-2945","authenticated-orcid":false,"given":"Jamil A.","family":"Buledi","sequence":"additional","affiliation":[{"name":"National Center of Excellence in Analytical Chemistry University of Sindh  Jamshoro Pakistan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anwar Ul","family":"Haq","sequence":"additional","affiliation":[{"name":"Key Laboratory of Optoelectronic Devices and Systems College of Physics and Optoelectronic Engineering Shenzhen University  Shenzhen P.\u2009R. 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