The invention relates to lithium-based battery systems and, more particularly, to electro-spinable solution compositions, electro-spun sulfur-polymer fibers, e.g., wires and yarns, and their use in preparing high performance sulfur mattes, e.g., electrodes, for lithium-sulfur batteries with potential applications in small-scale mobile devices. The sulfur-polymer fibers have nanoscale dimensions and yarn-like morphology. The sulfur-polymer fibers can be prepared by co-dissolving sulfur and polymer in a solvent for forming the electro-spinable solution, and electrospinning the solution. The electrospun fibers can be used to form a composite that includes alternating layers of the electrospun fibers and polymer on a current collector.