The interactions between counterions and electronic carriers in electrically doped semiconducting polymers are important for delocalization of charge carriers, electronic conductivity, and thermal stability. The introduction of a dianions in semiconducting polymers leads to double doping where there is one counterion for two charge carriers. Double doping minimizes structural distortions, but changes the electrostatic interactions between the carriers and counterions. Polymeric ionic liquids (PIL) with croconate dianions are helpful to investigate the role of the counterion in p‐type semiconducting polymers. PILs prevent diffusion of the cation into the semiconducting polymers during ion exchange. The redox‐active croconate dianions undergo ion exchange with doped semiconducting polymers depending on their ionization energy. Croconate dianions are found to reduce doped films of poly(3‐hexyl thiophene), but undergo ion exchange with a polythiophene with tetraethylene glycol side chains, P(g₄2T‐T), that has a lower ionization energy. The croconate dianion maintains crystalline order in P(g₄2T‐T) and leads to a lower activation energy for the electrical conductivity than PF₆⁻ counterions. The control of the doping level with croconate allows optimization of the thermoelectric performance of the semiconducting polymer. The thermal stability of the doped films of P(g₄2T‐T) is found to depend strongly on the nature of the counterion.