A new polymer acceptor, naphthodiperylenetetraimide‐vinylene (NDP‐V), featuring a backbone of altenating naphthodiperylenetetraimide and vinylene units is designed and applied in all‐polymer solar cells (all‐PSCs). With this polymer acceptor, a new record power‐conversion efficiencies (PCE) of 8.59% has been achieved for all‐PSCs. The design principle of NDP‐V is to reduce the conformational disorder in the backbone of a previously developed high‐performance acceptor, PDI‐V, a perylenediimide‐vinylene polymer. The chemical modifications result in favorable changes to the molecular packing behaviors of the acceptor and improved morphology of the donor–acceptor (PTB7‐Th:NDP‐V) blend, which is evidenced by the enhanced hole and electron transport abilities of the active layer. Moreover, the stronger absorption of NDP‐V in the shorter‐wavelength range offers a better complement to the donor. All these factors contribute to a short‐circuit current density (J _sc) of 17.07 mA cm⁻². With a fill factor (FF) of 0.67, an average PCE of 8.48% is obtained, representing the highest value thus far reported for all‐PSCs.