LAUSR

The strong and counterproductive interrelationship of thermoelectric parameters remains a bottleneck to improving thermoelectric performance, especially in polymer‐based materials. In this paper, a compositional range is investigated over which there is decoupling of the electrical conductivity and Seebeck coefficient, achieving increases in at least one of these two parameters while the other is maintained or slightly increased as well. This is done using an alkylthio‐substituted polythiophene (PQTS12) as additive in poly(bisdodecylquaterthiophene) (PQT12) with tetrafluorotetracyanoquinodimethane (F4TCNQ) and nitrosyl tetrafluoroborate (NOBF4) as dopants. The power factor increases two orders of magnitude with the PQTS12 additive at constant doping level. Using a second pair of polymers, poly(2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (PBTTTC12) and poly(2,5‐bis(3‐dodecylthiothiophen‐2‐yl)thieno[3,2‐b]thiophene, (PBTTTSC12), with higher mobilities, decoupling of the Seebeck coefficient and electrical conductivity is also observed and higher power factor is achieved. Distinguished from recently reported works, these two sets of polymers possess very closely offset carrier energy levels (0.05–0.07 eV), and the microstructure, assessed using grazing incidence X‐ray scattering, and mobility evaluated in field‐effect transistors, are not adversely affected by the blending. Experiments, calculations, and simulations are consistent with the idea that blending and doping polymers with closely spaced energy levels and compatible morphologies to promote carrier mobility favors increased power factors.