Abstract It is demonstrated that the n‐type thermoelectric performance of donor–acceptor (D–A) copolymers can be enhanced by a factor of &gt;1000 by tailoring the density of states (DOS). The DOS distribution is tailored by embedding sp 2 ‐nitrogen atoms into the donor moiety of the D–A backbone. Consequently, an electrical conductivity of 1.8 S cm −1 and a power factor of 4.5 µW m −1 K −2 are achieved. Interestingly, an unusual sign switching (from negative to positive) of the Seebeck coefficient of the unmodified D–A copolymer at moderately high dopant loading is observed. A direct measurement of the DOS shows that the DOS distributions become less broad upon modifying the backbone in both pristine and doped states. Additionally, doping‐induced charge transfer complexes (CTC) states, which are energetically located below the neutral band, are observed in DOS of the doped unmodified D–A copolymer. It is proposed that charge transport through these CTC states is responsible for the positive Seebeck coefficients in this n‐doped system. This is supported by numerical simulation and temperature dependence of Seebeck coefficient. The work provides a unique insight into the fundamental understanding of molecular doping and sheds light on designing efficient n‐type OTE materials from a perspective of tailoring the DOS.

N‐Type Organic Thermoelectrics of Donor–Acceptor Copolymers: Improved Power Factor by Molecular Tailoring of the Density of States