Hydrogen can be employed as an alternative renewable energy source in response to climate change, global warming, and the energy problem. Methanol gas steam reforming (SRM) is the major method used in industry to produce hydrogen. In the SRM process, the catalyst nature offers benefits such as low cost, simplicity, and quickness. In this work, delafossite copper yttrium oxide (CuYO2) nanofibers were successfully prepared by electrospinning. The prepared CuYO2 nanofibers have different physical and chemical properties including thermoelectric behavior. The electrospinning method was used to produce as-spun fibers and annealed in an air atmosphere to form Cu2Y2O5 fibers; then, Cu2Y2O5 fibers were annealed in a nitrogen atmosphere to form CuYO2 nanofibers. X-ray diffraction studies and thermogravimetric and transmission electron microscope analysis confirmed the formation of CuYO2 nanofibers. The CuYO2 nanofibers were applied to methanol steam reforming for hydrogen production to confirm their catalytic ability. The CuYO2 nanofibers exhibited high catalytic activity and the best hydrogen production rate of 1967.89 mL min−1 g-cat−1 at 500 °C. The highly specific surface area of CuYO2 nanofibers used in steam reforming reactions could have significant economic and industrial implications. The performance of these CuYO2 nanofibers in hydrogen generation could be very important in industries with a global economic impact. Furthermore, the H2 production performance increases at higher reaction temperatures.