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In this study, we proposed a dual\u2010path exciton harvesting strategy that combines high\u2010energy reverse intersystem crossing with triplet\u2013triplet annihilation to improve exciton utilization. The new deep\u2010blue emitter PChCz, based on the chrysene moiety, exhibits favorable high\u2010energy reverse intersystem crossing from high\u2010lying triplet states, enabling non\u2010doped OLEDs with a peak external quantum efficiency of 21.3%. To alleviate triplet\u2010polaron annihilation at elevated current densities, a co\u2010deposited sensitizer is employed to reutilize low\u2010energy triplet via the triplet\u2013triplet annihilation mechanism, thereby further improving the external quantum efficiency to 25.5% with suppressed roll\u2010off. Morphological analysis reveals that co\u2010deposition enhances compositional homogeneity and optimizes molecular orientation, which are conducive to efficient energy transfer and light outcoupling. Supported by rational molecular design and morphological control, the proposed dual\u2010path exciton harvesting mechanism presents an effective approach for the development of high\u2010performance deep\u2010blue OLEDs.<\/jats:p>","DOI":"10.1002\/adma.202517600","type":"journal-article","created":{"date-parts":[[2025,12,24]],"date-time":"2025-12-24T15:34:27Z","timestamp":1766590467000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Dual\u2010Path Exciton Harvesting Guided by Molecular Packing and Orientation Achieves Highly Efficient Deep\u2010Blue Emission"],"prefix":"10.1002","volume":"38","author":[{"given":"Yulong","family":"Li","sequence":"first","affiliation":[{"name":"Institute of Polymer Optoelectronic Materials and Devices Guangdong Basic Research Center of Excellence for Energy &amp; Information Polymer Materials State Key Laboratory of Luminescent Materials and Devices South China University of Technology  Guangzhou 510640 P. 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