Conjugation-break flexible spacers in-between π-conjugated segments were utilized herein toward processable perylene diimide (PDI)-based polymers. Aromatic-aliphatic PDI-based polymers were developed via the two-phase polyetherification of a phenol-difunctional PDI monomer and aliphatic dibromides. These polyethers showed excellent solubility and film-forming ability and deep lowest unoccupied molecular orbital (LUMO) levels (-4.0 to -3.85 eV), indicating the preservation of good electron-accepting character or characteristics, despite the non-conjugated segments. Their thermodynamic properties, local dynamics, and ionic conductivity demonstrate the suppression of PDI's inherent tendency for aggregation and crystallization, suggesting PDI-polyethers as versatile candidates for organic electronic applications. Their dynamics investigation using dielectric spectroscopy revealed weak dipole moments arising from the distortion of the planar perylene cores. Blends of the PDI-polyethers (as electron acceptors) with P3HT (as a potential electron donor component) showed UV-vis absorbances from 350 to 650 nm and a tendency of the PDI-polyethers to intertwine with rr-P3HT and restrain its high crystallization tendency.