The hydrogen evolution reaction (HER) is the central core of electrocatalysis and plays a crucial role in water splitting to obtain hydrogen. It has been inevitable to develop metal-free catalysts in terms of sustainability, the environment, and economic feasibility. Carbon-based materials, are called metal-free electrocatalysts, are regarded as one of the most critical candidates due to their abundant source, but they often show poor activity. The strategic aim of this study is to convert commercial carbon fiber into heteroatom-doped graphene-like surfaced fibers via an eco-friendly and fast intercalation/semi-exfoliation mechanism called Yucel’s method. Furthermore, X-ray photoelectron spectroscopy (XPS) verified that the intercalation has taken place successfully and that the heteroatoms (S, O) are doped to the graphene-like structure by covalent bonds. The catalysts with 1 M H2SO4 were illustrated superior HER performance compared to bare CF.