Significant enhancement of thermoelectric (TE) performance was observed for free-standing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) composite films obtained from a PEDOT:PSS aqueous solution by simultaneous addition of dimethyl sulfoxide (DMSO) and different concentrations of urea. The electrical conductivity was enhanced from 8.16 S cm−1 to over 400 S cm−1, and the maximum Seebeck coefficient reached a value of 18.81 μV K−1 at room temperature. The power factor of the PEDOT:PSS composite films reached 8.81 μW m−1 K−2. The highest thermoelectric figure of merit (ZT) in this study was 0.024 at room temperature, which is at least one order of magnitude higher than most polymers and bulk Si. These results indicate that the obtained composite films are a promising thermoelectric material for applications in thermoelectric refrigeration and thermoelectric microgeneration.