In the present work, structural and catalytic characterization was performed on La_0.6Sr_0.4MnO₃ (LSM) nanofibers. The LSM nanofibers were obtained using the electrospinning technique. For comparison, LSM powders with identical composition were characterized as well. The LSM powders were prepared through a self-combustion citrate-based procedure. SEM, EDX, XRD, and BET investigations were carried out on both LSM nanofibers and powders, pointing out the different structural features. The LSM nanofibers showed a higher surface area than the LSM powders and a lower presence of strontium oxide on the surface. Results of the H₂-Temperature Programmed Reduction (TPR) tests showed evidence of a higher reactivity of the nanofibers compared to the powders. The catalytic characterization was performed utilizing a methane oxidation activity test, revealing a better catalytic performance of the LSM nanofibers: at 800 °C. The methane conversion achieved with the LSM nanofibers was 73%, which compared well with the 50% obtained with powders at 900 °C.