Solid-contact ion-selective electrodes (SC-ISEs) with ionophore-based polymer-sensitive membranes have been the major devices in wearable sweat sensors toward electrolyte analysis. However, the toxicity of ionophores in ion-selective membranes (ISMs), for example, valinomycin (K + ion carrier), is a significant challenge, since the ISM directly contacts the skin during the tests. Herein, we report coating a hydrogel of graphene oxide-poly(vinyl alcohol) (GO-PVA) on the ISM to fabricate hydrogel-based SC-ISEs. The hydrogen bond interaction between GO sheets and PVA chains could enhance the mechanical strength through the formation of a cross-linking network. Comprehensive electrochemical tests have demonstrated that hydrogel-coated K + -SC-ISE maintains Nernstian response sensitivity, high selectivity, and anti-interference ability compared with uncoated K + -SC-ISE. A flexible hydrogel-based K + sensing device was further fabricated with the integration of a solid-contact reference electrode, which has realized the monitoring of sweat K + in real time. This work highlights the possibility of hydrogel coating for fabricating biocompatible wearable potentiometric sweat electrolyte sensors.