The performance of semiconducting polymers is strongly influenced by the structural arrangement of the polymer chains. Solvent-induced prestructuring of polymer chains may occur prior to polymer deposition, impacting device performance. We employed fluorescence techniques, including fluorescence correlation spectroscopy (FCS) and single-molecule fluorescence spectroscopy (smFS), to reveal chain conformations of P(NDI2OD-T2) in solutions and characterize aggregate types and sizes as they vary wit