The combination of dimethyl sulfoxide (DMSO)-solvent doping and physical-chemical DMSO/salt de-doping in a sequence has been used to improve the thermoelectric (TE) properties of poly(3,4-ethylenedioxythiophene):poly (4-styrenesulfonate) (PEDOT:PSS) films. A high power factor of ca.105.2 mu W m(-1) K-2 has been achieved for the PEDOT:PSS film after post-treatment with 10 % sodium sulfite (Na2SO3) in the DMSO/salt mixture (v/v), outperforming sodium bicarbonate (NaHCO3). The initial DMSO-doping treatment induces a distinct phase separation by facilitating the aggregation of the PEDOT molecules. At the same time, the subsequent DMSO/salt dedoping post-treatment strengthens the selective removal of the surplus non-conductive PSS chains. Substantial alterations in the oxidation level, chain conformations, PEDOT crystallites and their preferential orientation are observed upon treatment on the molecular level. At the mesoscale level, the purification and densification of PEDOT-rich domains enable the realization of inter-grain coupling by the formation of the electronically well-percolated network. Thereby, both electrical conductivity and Seebeck coefficient are optimized.