Abstract: | Low n‐doping efficiency and inferior stability restrict the thermoelectric performance of n‐type conjugated polymers, making their performance lag far behind of their p‐type counterparts. Reported here are two rigid coplanar poly(p‐phenylene vinylene) (PPV) derivatives, LPPV‐1 and LPPV‐2 , which show nearly torsion‐free backbones. The fused electron‐deficient rigid structures endow the derivatives with less conformational disorder and low‐lying lowest unoccupied molecular orbital (LUMO) levels, down to ?4.49 eV. After doping, two polymers exhibited high n‐doping efficiency and significantly improved air stability. LPPV‐1 exhibited a high conductivity of up to 1.1 S cm?1 and a power factor as high as 1.96 μW m?1 K?2. Importantly, the power factor of the doped LPPV‐1 thick film degraded only 2 % after 7 day exposure to air. This work demonstrates a new strategy for designing conjugated polymers, with planar backbones and low LUMO levels, towards high‐performance and potentially air‐stable n‐type polymer thermoelectrics. |