Graphene oxide/ carbon nanotubes (GO/CNTs) aerogels were prepared by adjusting the proportion of GO and CNTs, the corresponding reduced graphene oxide/CNTs (rGO/CNTs) aerogels were obtained by thermal reduction. Then, poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT: PSS) was compounded with rGO/CNTs aerogels at a mass ratio of 1:1 to prepare rGO/CNTs/PEDOT: PSS (GCP) composites. Structural analyses revealed the strong π-π interaction between rGO/CNTs and PEDOT: PSS, which leads to the formation of ordered regions. Porous structures of rGO/CNTs aerogels act as conductive network skeleton to promote carrier transport in GCP composites, and the electrical conductivity of GCP composites improves effectively. The optimal electrical conductivity and Seebeck coefficient of GCP5 were 1788.11 S cm−1 and 15.87 μV K−1 respectively. The maximum power factor and ZT merit of GCP5 achieved to 45.03 μW m−1 K−2 and 2.65 × 10−2 at room temperature, which was almost 43 and 17 times than that of PEDOT: PSS.