AbstractA series of tin‐organic frameworks materials (SnMOF) were synthesized using different organic linkers, including phthalic acid, isophthalic acid, 1,4‐dicarboxybenzene, and 1,3,5‐benzenetricarboxylic acid. The structure and morphology of SnMOF were characterized by Fourier Transform infrared spectroscopy (FT‐IR), X‐ray diffraction, N2 adsorption/desorption isortherm (BET), scanning electron microscope‐Energy Dispersive System (EDS), and Thermogravimetry (TG). Taking together, these experimental results indicated that the different types and amounts of COOH in organic linkers have a significant effect on the physical properties of SnMOF. Among them, carbon‐supported SnMOF as catalysts for acetylene hydrochlorination features the considerable activity and vinyl chloride selectivity. Such excellent performance is attributed to the fact that 1,3,5‐benzenetricarboxylic acid can effectively strengthen the interaction effect between C2H2 and Sn‐O‐C, according to the results of C2H2‐TPD, HCl adsorption experiments, and X‐ray photoelectron spectroscopy (XPS).