Extremely simplified one-step roll-to-roll slot-die-printed flexible indium tin oxide (ITO)-free polymer solar cells (PSCs) are demonstrated based on the ternary blends of electron-donor polymer thieno[3,4-b]thiophene/benzodithiophene, electron-acceptor fullerene [6,6]-phenyl-C-71-butyric acid methyl ester, and electron-extracting polymer poly[(9,9-bis(3-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) at room temperature (RT) in ambient air. The flexible ITO-free PSC exhibits a comparable power conversion efficiency (PCE) with the device employing complicated two-step slot-die printing (5.29% vs 5.41%), which indicates that PFN molecules can migrate from the ternary nanocomposite toward the Ag cathode via vertical self-assembly during the one-step slot-die printing process in air. To confirm the migration of PFN, the morphology and elemental analysis as well as charge transport of different active layers are investigated by the in situ transient film drying process, transmission electron microscopy, atomic force microscopy, contact angle and surface energy, X-ray photoelectron spectroscopy, scanning electron microscopy, impedance spectroscopy, transient photovoltage and transient photocurrent, and laser-beam-induced current. Moreover, the good air and mechanical stability of the flexible device with a decent PCE achieved in 1 cm(2) PSCs at RT in air suggests the feasibility of energy-saving and time-saving one-step slot-die printing to large-scale roll-to-roll manufacture in the future.