Recently, considerable attention has been paid to the development of new functionalized polymers to improve the fuel efficiency of vehicles by reducing the rolling resistance of tires to adhere to strict CO2 emission regulations. Accordingly, multifunctionalized (MF) reversible addition–fragmentation chain transfer (RAFT) emulsion styrene–butadiene rubbers (ESBR) were synthesized, in which chain-end and in-chain functionalization were performed simultaneously by introducing a third monomer (glycidyl methacrylate; GMA) using RAFT polymerization. Compared with GMA ESBR, in which GMA is introduced as a third monomer by conventional radical polymerization (CRP), there was an even distribution of GMA per chain in the MF-RAFT ESBR. After preparing the silica-filled compounds, vulcanizate structure analysis and mechanical property evaluation of the compounds were performed. The MF-RAFT ESBR prepared by RAFT polymerization exhibited superior in-chain functionalization efficiency compared with GMA ESBR prepared by CRP because of the even distribution of GMA and higher crosslink density. Consequently, MF-RAFT ESBR compound showed superior silica dispersion, abrasion resistance, and lower rolling resistance compared with the GMA ESBR compound.