A n‐type conjugated polymer containing naphthalene diimide (NDI) and 1,3,4‐thiadiazole (TZ) moieties, named PNTZ, has been synthesized and applied for all‐polymer solar cells (all‐PSCs). By the incorporation of TZ unit into the polymer main chains, the lowest unoccupied molecular orbital level of this polymer has been adjusted effectively. In addition, the electron‐acceptor PNTZ shows a broad absorption spectrum in the range of 300–700 nm, and possesses complementary absorption spectrum with the electron‐donor PTB7‐Th. On the basis of PNTZ as the acceptor and PTB7‐Th as the donor, the all‐PSCs are fabricated. After optimization, the well blend morphologies with a continuous D/A interpenetrating network are observed and the best all‐PSC device exhibits a power conversion efficiency of 4.35% with a high short‐circuit current density of 13.26 mA cm−2. This research demonstrates that the TZ‐containing polymer PNTZ is a promising non‐fullerene acceptor for high efficiency all‐PSCs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 990–996