A series of alkylorganotin-based catalysts (Sn-g-C3N4/AC) was prepared by wet impregnation in ethanol using different g-C3N4 precursors and alkylorganotin compounds. The structure, texture, surface composition, and adsorption properties of the as-prepared catalysts were extensively characterized. Then, the obtained samples were evaluated for their catalytic performance in hydrochlorination of acetylene. The results provided by the X-ray photo-electron spectroscopy, acetylene temperature-programmed desorption, and HCl adsorption confirmed the nature of the active sites (i.e. Sn-N-x) involved in the reactant adsorption, and hence in the improved catalytic performance. These active sites were also related to the improved lifetime of alkylorganotin-based catalysts in the hydrochlorination of acetylene. At a constant reaction temperature of 200 degrees C with an acetylene gas hourly space velocity (C2H2-GHSV) of 30 h(-1), Sn-g(1)-C3H4/AC-550 exhibited the highest acetylene conversion (similar to 98.0%) and selectivity toward the vinyl chloride monomer (>98.0%). From the catalytic test results, it was reasonably concluded that the hexamethylenetetramine is the most suitable N precursor, as compared to the dicyandiamide and urea, to prepare high-performance catalysts. From the BET specific surface area of fresh and used catalysts, it was suggested that, in contrast to dicyandiamide and urea, hexamethylenetetramine could delay the deposition of coke on alkylorganotin-based catalysts, which is reflected by the extended lifetime.