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In this work, a series of PhnSnCl4-n (n = 1, 2, 3, and 4) based catalysts were prepared by incipient wetness impregnation using activated carbon (AC) as support and triphenyltin chloride (Ph3ClSn) and tin(IV) chloride (SnCl4) as Sn precursors. The obtained catalysts were systematically characterized by X-ray diffraction (XRD), N2 physisorption, Scanning electron microscope (SEM), Thermogravimetric analysis (TG-DTG), and Inductively coupled plasma (ICP) analytical techniques. The catalytic performance of the prepared PhnSnCl4-n samples was evaluated in the acetylene hydrochlorination reaction. When a gas hourly space velocity (GHSV, C2H2 based) and a reaction temperature of 30 h-1 and 200 ºC, respectively were used for the reaction performed over the 12% (1.0Ph3ClSn+3.5SnCl4)/AC-200 catalyst, an acetylene conversion of 98.0% with a selectivity to vinyl chloride of 98.5% were obtained. These results demonstrated that PhnSnCl4-n can effectively improve the catalytic activity and prolong the lifetime of SnCl4/AC catalysts. Moreover, by comparing with HgCl2/AC, PhnSnCl4-n-based catalysts exhibit much enhanced catalytic activity in the hydrochlorination of acetylene. It is assumed that the outstanding activity is due to trichlorophenylstannane (PhCl3Sn) active sites, resulted from the organotin redistribution reaction between Ph3ClSn and SnCl4. In addition, such sites also improved the SnCl4/AC catalyst stability during the reaction.