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While carboxylate\u2010functionalized polymers have shown considerable promise, the influence of different carboxylate substitution positions on device performance remains poorly understood. In this work, we designed and synthesized two polymeric isomers (2TC\u2010F and TTC\u2010F) to systematically investigated the effects of connecting the carboxylate side chain at different sites of the thiophene (T) and thieno[3,4\u2010b]thiophene (TT) units on the energy level structure, molecular packing behavior, hole mobility, and charge transfer properties at the perovskite\/HTM interface. The study demonstrates that, compared to 2TC\u2010F, TTC\u2010F exhibits better energy level alignment, higher planarity, and more effective defect passivation. As a result, TTC\u2010F\u2010based CsPbI\n                    <jats:sub>2<\/jats:sub>\n                    Br PSCs achieved a power conversion efficiency (PCE) of 17.58%, significantly outperforming the 2TC\u2010F\u2010based device (14.54%), along with excellent stability under thermal aging and ambient storage. When integrated into perovskite\/organic tandem solar cells (TSCs), the TTC\u2010F\u2010based device reached a PCE of 23.29%. This work highlights the importance of site\u2010specific side\u2010chain engineering in designing high\u2010performance HTMs.\n                  <\/jats:p>","DOI":"10.1002\/advs.202524013","type":"journal-article","created":{"date-parts":[[2026,2,15]],"date-time":"2026-02-15T12:04:26Z","timestamp":1771157066000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Site\u2010Specific Carboxylate Functionalization in Conjugated Hole Transport Polymers Enables Efficient CsPbI\n                    <sub>2<\/sub>\n                    Br Single\u2010Junction and Tandem Solar Cells"],"prefix":"10.1002","volume":"13","author":[{"given":"Jingfei","family":"Wang","sequence":"first","affiliation":[{"name":"Henan Institute of Advanced Technology Zhengzhou University  Zhengzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weilin","family":"Zhang","sequence":"additional","affiliation":[{"name":"Henan 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