A new synthesis method for organic–inorganic hybrid Poly(vinylidene fluoride)-SiO2 cation-change membranes (CEMs) is proposed. This method involves mixing tetraethyl orthosilicate (TEOS) and 3-mercapto-propyl-triethoxy-silane (MPTES) into a polyvinylidene fluoride (PVDF) sol-gel solution. The resulting slurry was used to prepare films, which were immersed in 0.01 M HCl, which caused hydrolysis and polycondensation between the MPTES and TEOS. The resulting Si-O-Si polymers chains intertwined and/or penetrated the PVDF skeleton, significantly improving the mechanical strength of the resulting hybrid PVDF-SiO2 CEMs. The -SH functional groups of MPTES oxidized to-SO3H, which contributed to the excellent permeability of these CEMs. The surface morphology, hybrid structure, oxidative stability, and physicochemical properties (IEC, water uptake, membrane resistance, membrane potential, transport number, and selective permittivity) of the CEMs obtained in this work were characterized using scanning electron microscope and Fourier transform infrared spectroscopy, as well as electrochemical testing. Tests to analyze the oxidative stability, water uptake, membrane potential, and selective permeability were also performed. Our organic–inorganic hybrid PVDF-SiO2 CEMs demonstrated higher oxidative stability and lower resistance than commercial Ionsep-HC-C membranes with a hydrocarbon structure. Thus, the synthesis method described in this work is very promising for the production of very efficient CEMs. In addition, the physical and electrochemical properties of the PVDF-SiO2 CEMs are comparable to the Ionsep-HC-C membranes. The electrolysis of the concentrated CoCl2 solution performed using PVDF-SiO2-6 and Ionsep-HC-C CEMs showed that at the same current density, Co2+ production, and current efficiency of the PVDF-SiO2-6 CEM membrane were slightly higher than those obtained using the Ionsep-HC-C membrane. Therefore, our novel membrane might be suitable for the recovery of cobalt from concentrated CoCl2 solutions.