The development of low-cost and highly efficient hydrogen evolution reaction (HER) catalysts has driven continuous effort. Here we develop a one-step preparation method of novel two-dimensional coupled hybrid of molybdenum carbide embedded N-doped carbon nanolayer architecture (MoCx-N/CNL) using cheap cotton as carbon and nitrogen precursor and ammonium molybdate as Mo precursor. Transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), energy dispersive X-ray spectra (EDS), scanning electron microscopy (SEM), element mapping, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were utilized to characterize the as-prepared nanocomposites. The synergistic effect between dispersive Mo2C particles and N doping in MoCx-N/CNL leads to remarkable HER performance in acidic media. Different amount of Mo were doped in the samples by arranging the ammonium molybdate concentration. Three samples were obtained and MoCx-N/CNL-3 showed better HER electrocatalytic performance than other two samples. Moreover, the as prepared MoCx-N/CNL-3 exhibits excellent stability and durability in acidic media. A new viable route is provided to prepare molybdenum carbide embedded N-doped carbon hybrid architecture with higher HER stability and activity, it is of significance in novel HER catalyst preparation.