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Solvent vapor annealing (SVA) is an essential post\u2010treatment strategy for controlling active layer morphology. However, most current SVA are conducted ex situ, limiting their ability to accurately reveal the morphological evolution of active layers of APSCs. In this study, in situ synchrotron radiation GIWAXS and in situ UV\u2013vis spectroscopy combined with GISAXS is used to monitor the morphological evolution of PM6\/PY\u2010IT blends during the SVA process in real\u2010time. Results showed that the PY\u2010IT absorption peak exhibited a red shift under a nonpolar carbon disulfide vapor, while a blue shift is observed during the SVA process with a polar chloroform vapor. The SVA process can be divided into three stages: solvent swelling, recrystallization, and molecular rearrangement. For thermally pre\u2010annealed samples subjected to chloroform SVA, the power conversion efficiency (PCE) increased by 15.1%. The improved PCE stems from reduced crystal plane spacing (d\u2010spacing), enhanced crystal coherence length, and optimal phase separation via SVA. Pre\u2010annealing suppresses excessive swelling, emphasizing the reordering dynamical role in the morphology of APSCs. This study offers insights into balancing SVA conditions to maximize performance and minimize adverse effects.<\/jats:p>","DOI":"10.1002\/advs.202501823","type":"journal-article","created":{"date-parts":[[2025,6,23]],"date-time":"2025-06-23T14:39:51Z","timestamp":1750689591000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Real\u2010Time Probing of Morphological Evolution and Recrystallization During Solvent Annealing in Blade\u2010Coated All\u2010Polymer Organic Solar Cells Using In Situ X\u2010Ray Scattering"],"prefix":"10.1002","volume":"12","author":[{"given":"Jialiang","family":"Hao","sequence":"first","affiliation":[{"name":"Shanghai Synchrotron Radiation Facility Shanghai Advanced Research Institute Chinese Academy of Sciences  Shanghai 201204 China"},{"name":"School of Chemical Engineering and Technology Taiyuan University of Science and Technology  Taiyuan 030027 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