In the present communication, we report on recent researches for optimizing the performance of a primary organic-based Li-air cell. These researches focus on new processing technologies for a high capacity and high rate capable carbon cathode, and the development of oxygen selective membranes based on polysiloxane and methacrylate–polysiloxane copolymers. These membranes, generally classified as silicone rubbers exhibit high permeability for oxygen and impede water transport from the atmosphere into the Li-air cell and solvent loss from the cell into the atmosphere.