N-Doped mesoporous carbon extrudate with a major quaternary N species has been successfully prepared through direct carbonization of wheat flour/gluten with silica, which is a cheap and convenient method for scale-up production approach. The obtained carbon extrudate metal-free catalyst enables highly efficient production of vinyl chloride monomer through acetylene hydrochlorination, with a superior catalytic performance and excellent stability (>85% conversion and vinyl chloride selectivity over 99% at 220 °C).