We develop three types of organic–inorganic composite membranes based on a semi-interpenetrating polymer network (SIPN) to explore the effects of membrane structure on the possible operating current densities of a non-aqueous redox flow battery (RFB) system. Poly(vinylidene fluoride) (PVdF) is selected as a supporting polymer matrix for improving the chemical and thermal stability of the organic–inorganic composite membranes. We also introduce silica nanoparticles (5 wt% of PVdF) into the membranes to ensure the low crossover of active species. The fabrication of SIPN through the addition of glycidyl methacrylate, 4-vinylpyridine, or N-vinylcarbazole enables control of the membrane structure. Depending on monomer type, the membrane structure is determined to be either aliphatic or aromatic in terms of chemical properties and either dense or porous in terms of physical properties. These chemical and physical structures affect the electrochemical properties that correspond to charge/discharge performance and to the range of possible operating current densities. An important requirement is to examine charge/discharge performance at the possible range of operating current densities by using various membrane structures. This requirement is discussed in relation to a proposed design strategy for non-aqueous RFB membranes.