ABSTRACTTwo miktoarm star‐shaped rubbers with large‐volume functional groups of 1,1‐diphenylhexyl at the ends of arms (DMS–PB–SBR) and one miktoarm star‐shaped rubber with n‐butyl groups at the ends of arms (BMS–PB–SBR) were prepared by 1,1‐diphenylhexyllithium (DPHLi) and n‐butyl lithium as initiators, respectively. The molecular structures and morphological properties of the three rubbers (MS–PB–SBR) were studied and compared with those acquired from the blend consisting of star‐shaped solution‐polymerized butadiene styrene rubber (S‐SSBR) and butadiene rubber (PBR) prepared by ourselves. The results showed that MS–PB–SBR exhibited a more uniform distribution of PBR phase and a smaller phase size of PBR than that of S‐SSBR/PBR blend. It is found that MS–PB–SBR composites filled with CB showed the lower Payne effect than that of S‐SSBR/PBR/CB composite, suggesting that the MS–PB–SBR/CB composite (particularly the DMS–PB–SBR/CB composites) would possess excellent mechanical properties, high wet‐skid resistance, and low rolling resistance. For the studied MS–PB–SBR systems, the contribution of large‐volume functional groups at the end of PBR molecular chains to decrease the rolling resistance was larger than that of Sn coupling effect. It is envisioned that the miktoarm star‐shaped rubbers with 1,1‐diphenylhexyl groups at the molecular ends would be useful for making treads of green tires. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40002.