Abstract: Heat dissipation has become an essential factor affecting the performance and operating life of electronic devices as the development of modern electronic devices continues to miniaturize and integrate to increase power density. The development of new thermal interface materials has been the key solution to heat dissipation. Herein, a high thermal conductive graphene-based hydrogel (G/PVP-PVA) with an interpenetrating network is successfully constructed by physical cross-linking combined with the freeze–thaw process. The effect of the preparation parameters on its all-around performance is evaluated in detail. When the graphene dosage is 0.33%, the maximal tensile stress of the hydrogel is 322.4 kPa, the self-recovery is 95.4%, and the thermal conductivity is as high as 1.486 W m−1 K−1. The cooling simulation experiment shows that the hydrogel can adhere closely to the wall to reduce the air thermal resistance effectively, and the cooling rate is as high as 5.04 °C min−1. The simulation experiment of the human body cooling shows that its cooling rate is 1.10 °C min−1, while that for a commercial hydrogel is 0.27 °C min−1. The G/PVP-PVA can give a practically potential solution for the thermal management of flexible electronic products and provides a new material for an efficient medical cooling application.