Lightweight and flexible biosensors that can sustain mechanical deformation and can be adhered to human skin is an interesting field of study. In the current article, a systematic study on development of thermally exfoliated graphene oxide (TEGO)–reinforced poly(vinyl alcohol) (PVA)–based conductive hydrogel nanocomposites has been reported. The free‐standing hydrogels were synthesized using controlled and repetitive freeze‐thaw cycles. The samples were then studied for their mechanical as well as electrical properties. The hydrogels were characterized for their microstructural, chemical, and rheological properties to understand the observed macroscopic properties. Additionally, a study on the behavior of hydrogels immersed in phosphate‐buffered saline (PBS) was carried out to investigate their hydrolytic stability within simulated biological environment. Overall, the nanocomposite hydrogels demonstrated excellent static and dynamic mechanical performance, stability in PBS, considerable electrical conductivity, and significant electrical response to applied external stress, establishing their potential for use as flexible biosensors.