Hydrogels have attracted extensive attention for their promising applications as flexible sensors. Developing conductive hydrogels with excellent mechanical properties still remains a significant challenge. Herein, double-network (DN) hydrogels composed of poly(vinyl alcohol) (PVA) and poly(ionic liquids) (PILs) are prepared through repetitive freezing/thawing process. The hydrogels are further treated with Fe3+ ions to enhance the mechanical properties due to the complexation between carboxyl groups and Fe3+ ions. The influence of the amount of PILs and concentration of Fe3+ on mechanical properties and conductivity is investigated. The optimal DN hydrogel P(VMCA-AA)1/PVA-Fe3+4 shows excellent mechanical properties, whose tensile strength, elongation at break, and toughness are 2.2 MPa, 350%, and 3.5 MJ m−3, respectively. P(VMCA-AA)1/PVA-Fe3+4 also displays a good conductivity of 1.04 S m−1. Moreover, the hydrogel demonstrates a high sensing sensitivity with a gauge factor (GF) of 3.36, indicating its application potential as a flexible sensor.