The article describes the preparation of polyvinyl alcohol (PVA)/polybutylene succinate (PBS)/lithium chloride (LiCl) hydrogels, their structural features, as well as their electrical and mechanical properties. Firstly, by using a twin screw extruder, the PBS was blended with plasticized PVA and then PBS fibres were formed during the process. Secondly, the PVA/PBS composite materials were dissolved in the binary mixed solvent of glycerol and water containing LiCl to prepare PVA/PBS/LiCl hydrogels by the sol-gel method. The morphology, structure, mechanical property, and conductivity of the hydrogels were investigated. The mechanical property of the hydrogels is improved with PBS fibres significantly and LiCl can improve the electrical conductivity of the hydrogels. The strength and conductivity of the PVA/PBS/LiCl (3 wt%) hydrogels are 4.67 MPa and 8.3 s/m, respectively. The PVA/PBS/LiCl hydrogels show good mechanical strength and conductivity and can be used in the wearable sensor field.