A new cathode material, FeS2-decorated carbon nanofiber (CNF), is proposed for Li-S batteries. The structure and physicochemical properties of the material have been engineered to enhance the poor cycling stability typically displayed by sulfur composites. The composite material shows a complex architecture with a matrix of CNF hosting the sulfur and core-shell FeS2 nanoparticles acting as a catalyst for a solid phase conversion-type reaction. This cathode delivers high discharge capacities of 864, 798, 689, 595 and 455 mAhg−1 at C/10, C/5, C/2, 1C and 2C, respectively, with a stable capacity retention of 87% at 2C after 300 cycles. FeS2-decorated CNF has been characterised using several techniques, including in-situ battery measurements at the ALBA synchrotron facility and high-throughput microscopy, giving valuable insights into its charge/discharge reaction mechanism. The excellent performance obtained is combined with the use of just low-cost and abundant elements such as iron, sulfur and carbon, which makes this battery highly promising for the next generation of electrochemical energy storage devices.