Abstract Hybrids of poly(3,4-ethylenedioxythiophene) (PEDOT):poly(4-styrene sulfonate) (PSS)/multi-walled carbon nanotube (MWCNT)/graphene (P/M/G), which have high electrical conductivity and low thermal conductivity, were successfully prepared in aqueous solution through in situ polymerization of 3,4-ethylenedioxythiophene (EDOT) monomers in the presence of poly(sodium 4-styrene sulfonate) (PSSNa). Meanwhile, the composites were characterized by Raman spectroscopy, infrared (IR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy. Thermoelectric properties of the samples were measured at room temperature and 50°C. Compared with pristine PEDOT:PSS (P), PEDOT:PSS/MWCNT (P/M) and PEDOT:PSS/graphene (P/G), the power factor of P/M/G composites was significantly improved, whatever the temperature. It increased from 0.061 μW/mK² to 0.105 μW/mK² at room temperature and from 0.070 μW/mK² to 0.142 μW/mK² at 50°C, meaning 72% and 103% enhancement, respectively. The increased power factor is attributed to the synergic effects of MWCNT and graphene, a hybrid structure with excellent electronic coupling and more electric channels.