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Experimental and computational results agree that the primary pathway involves double dehydrochlorination producing 1,3\u2010butadiene and HCl. Minor radical channels are evidenced by the detection of chloromethyl, methyl, and propargyl radicals in thermal decomposition, while chlorine radicals are absent. HZSM\u20105 zeolites lower the reaction temperature and facilitate 1,3\u2010butadiene association reactions producing C<jats:sub>5<\/jats:sub>\u2013C<jats:sub>12<\/jats:sub> olefins. Further reaction steps, detected experimentally and in part isomer\u2010selectively, mimic previously postulated cross\u2010linking pathways to aromatics in PVC catalytic pyrolysis. This study identifies C\uf8ffC coupling as well as Diels\u2013Alder dimerization of butadiene to yield polymethylated cyclopentadienes. These are central precursors to aromatics, for example, benzene, toluene, and xylenes (BTX). Ring expansion and contraction as well as transmethylation reactions are found to be dominant routes to aromatic products. The mechanisms during thermocatalytic conversion of PVC are applicable to other plastics and resemble the chemistry upon methanol\u2010 and methylchloride\u2010to\u2010hydrocarbon and aromatics conversion, which will inspire new strategies to enhance selectivity towards aromatics and mitigate coke formation.<\/jats:p>","DOI":"10.1002\/cssc.202500516","type":"journal-article","created":{"date-parts":[[2025,5,5]],"date-time":"2025-05-05T10:50:44Z","timestamp":1746442244000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Pathways to Aromatics in the Catalytic Pyrolysis of a Polyvinylchloride Model Compound Revealed by Operando Photoelectron Photoion Coincidence Spectroscopy"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0009-0002-7225-6200","authenticated-orcid":false,"given":"Jovanni","family":"Cabana","sequence":"first","affiliation":[{"name":"Paul Scherrer Institute  5232 Villigen Switzerland"},{"name":"Department of Chemistry and Applied Biosciences Institute for Chemical and Bioengineering  ETH Zurich 8093 Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5106-2656","authenticated-orcid":false,"given":"Zihao","family":"Zhang","sequence":"additional","affiliation":[{"name":"Paul Scherrer Institute  5232 Villigen Switzerland"},{"name":"Center for Renewable Carbon, School of Natural Resources University of Tennessee  Knoxville TN 37996 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2502-9454","authenticated-orcid":false,"given":"Zeyou","family":"Pan","sequence":"additional","affiliation":[{"name":"Paul Scherrer Institute  5232 Villigen Switzerland"},{"name":"Department of Chemistry and Applied Biosciences Institute for Chemical and Bioengineering  ETH Zurich 8093 Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pawan","family":"Kumar","sequence":"additional","affiliation":[{"name":"Paul Scherrer Institute  5232 Villigen Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8515-3302","authenticated-orcid":false,"given":"Xiangkun","family":"Wu","sequence":"additional","affiliation":[{"name":"Paul Scherrer Institute  5232 Villigen Switzerland"},{"name":"Environment Research Institute Shandong University  Qingdao 266237 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2742-1051","authenticated-orcid":false,"given":"Andras","family":"Bodi","sequence":"additional","affiliation":[{"name":"Paul Scherrer Institute  5232 Villigen Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2915-2553","authenticated-orcid":false,"given":"Gustavo A.","family":"Garcia","sequence":"additional","affiliation":[{"name":"Synchrotron SOLEIL L\u2019Orme des Merisiers  St. Aubin,BP 48 91192 Gif\u2010sur\u2010Yvette France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yang","family":"Shen","sequence":"additional","affiliation":[{"name":"School of Mechanical Engineering Shanghai Jiao Tong University  Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0004-0769-353X","authenticated-orcid":false,"given":"Xintong","family":"Xiao","sequence":"additional","affiliation":[{"name":"School of Mechanical Engineering Shanghai Jiao Tong University  Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Ma","sequence":"additional","affiliation":[{"name":"National Synchrotron Radiation Laboratory University of Science and Technology of China  Hefei Anhui 230029 P. 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