Van der Waals type forces are generally responsible for the stability of conjugated polymer–acceptor complexes, and no charge transfer is observed in the ground state. Electron transfer generally occurs from donor materials to acceptor materials via photoinduced electron transfer. Here, we report a partial ground-state charge transfer in the all-polymer donor–acceptor interface using density functional theory-based methods such as long-range corrected ωB97XD and hybrid meta exchange–correlation M06 functionals. These methods are also used to evaluate the geometrical and electronic properties of conjugated polymers in the neutral and charged states.