Electrical and thermal transportation properties of a novel structured 3D CNT network have been systematically investigated. The 3D CNT net work maintains extremely low thermal conductivity of only 0.035 W/(m K) in standard atmosphere at room temperature, which is among the lowest compared with other reported CNT macrostructures. Its electrical transportation could be adjusted through a convenient gas-fuming doping process. By potassium (K) doping, the original p-type CNT network converted to n-type, whereas iodine (I ) doping enhanced its electrical conductivity. The self-sustainable homogeneous network structure of as-fabricated 3D CNT network made it a promising candidate as the template for polymer composition. By in situ nanoscaled composition of 3D CNT network with polyaniline (PANI), the thermoelectric performance of PANI was significantly improved, while the self-sustainable and flexible structure of the 3D CNT network has been retained. It is hoped that as-fabricated 3D CNT network will contribute to the development of low-cost organic thermoelectric area. © 2011 American Chemical Society.