The search for non-noble metal catalysts with high activity for the hydrogen evolution reaction (HER) is crucial for efficient hydrogen production at low cost and on a large scale. Herein, we report a novel WO3-x catalyst synthesized on carbon nanofiber mats (CFMs) by electrospinning and followed by a carbonization process in a tubal furnace. The morphology and composition of the catalysts were tailored via a simple method, and the hybrid catalyst mats were used directly as cathodes to investigate their HER performance. Notably, the as-prepared catalysts exhibit substantially enhanced activity for the HER, demonstrating a small overpotential, a high exchange current density, and a large cathodic current density. The remarkable electrocatalytic performances result from the poor crystallinity of WO3-x, the high electrical conductivity of WO3-x, and the use of electrospun CNFs. The present work outlines a straightforward approach for the synthesis of transition metal oxide (TMO)-based carbon nanofiber mats with promising applications for the HER.