By the introduction of different building blocks and side‐chains, a series of donor–acceptor type polymer acceptors containing naphthalene diimide have been successfully prepared. The theoretical and experimental results show that the molecular design effectively tunes the energy levels, solubility, and coplanarity of the acceptor polymers. The intermolecular packing, which has been considered as a key factor in the bulk heterojunction morphology, has been adjusted by changing the coplanarity. As a result of improved morphology and fine‐tuned energy levels, a power conversion efficiency of 6.0% has been demonstrated for the optimized devices, which is among the highest‐efficiencies for reported all‐polymer solar cells. The improved device performance may be attributed to the resemble crystallinity of the donor/acceptor polymers, which can lead to the optimal phase separation morphology balancing both charge transfer and transport.