Branched polystyrene was first obtained via a reversible addition-fragmentation chain transfer (RAFT) process in the presence of chain transfer monomer p-vinyl benzene sulfonyl chloride (VBSC) in benzene at $60^{circ}C$ with 2-(ethoxycarbonyl)prop-2-yl dithiobenzoate as the RAFT agent and 2,2-azobisisobutyronitrile as an initiator. During the RAFT polymerization, VBSC played the role of branching agent. It could not only copolymerized but also acted as a chain transfer agent due to the polymerizable vinyl group and sulfonyl chloride chain transfer group in the VBSC. Gel permeation chromatography (GPC) traces demonstrated that the number-average molecular weights and molecular weight distributions increased along with monomer conversion. Compared with the RAFT process without VBSC, the resulting polymers had broad molecular weight distributions and the sulfonyl functionality of the resultant polymer at the branching point, indicating the formation of branched polystyrene. The structure of the obtained polystyrene was further analyzed by proton nuclear magnetic resonance ($^1H$ NMR) spectroscopy. The findings indicated that the branched polystyrene was mainly formed via the RAFT copolymerization of VBSC and styrene firstly to form polystyrene bearing pendant sulfonyl chloride group, and then the pendant sulfonyl chloride group acted as the chain transfer agent to generate the branched structure. In addition, the degree of branching and VBSC unit in copolymer increased along with the VBSC in the feed, implying that composition and structure of the branched polystyrenes could be tuned by the amount of VBSC in the feed.