This work describes the fabrication of hierarchical 3D Nafion enhanced carbon aerogels (NECAGs) for sensing applications via a fast freeze drying method. Graphene oxide, multiwalled carbon nanotubes and Nafion were mixed and extruded into liquid nitrogen followed by the removal of ice crystals by freeze drying. The addition of Nafion enhanced the mechanical strength of NECAGs and effective control of the cellular morphology and pore size was achieved. The resultant NECAGs demonstrated high strength, low density, and high specific surface area and can achieve a modulus of 20 kPa, an electrical conductivity of 140 S m-1, and a specific capacity of 136.8 F g-1 after reduction. Therefore, NECAG monoliths performed well as a gas sensor and as a biosensor with high sensitivity and selectivity. The remarkable sensitivity of 8.52 × 103 μA mM-1 cm-2 was obtained in dopamine (DA) detection, which is two orders of magnitude better than the literature reported values using graphene aerogel electrodes made from a porous Ni template. These outstanding properties make the NECAG a promising electrode candidate for a wide range of applications. Further in-depth investigations are being undertaken to probe the structure-property relationship of NECAG monoliths prepared under various conditions.