Thermoplastic polyurethane/graphene aerogel (TPU/GA) composites were fabricated by two steps as follows. Firstly, GA was used as network framework and prepared through freeze-drying and thermal reduction using poly vinyl alcohol (PVA) as crosslinking agent. And then TPU was impregnated in GA under vacuum condition. The microstructure of GA and TPU/GA as well as the influence of the content of PVA on the microstructure and electrical conductivity of the TPU/GA composites were investigated. The results demonstrate that GA exhibits 3D network structure and great electrical conductivity, and the TPU layers are wrapped around the network of GA. TPU/GA composites also exhibit good compressibility and electrical conductivity. With the increase of PVA content, the microstructure is more regular, and the conductive network connectivity of GA is improved, which results in higher electrical conductivity of GA and TPU/GA. While the mass of PVA is 5 times of GO, the electrical conductivity of manufactured TPU/GA composites is 58 S/m.