The compatibility between solution polymerized styrene–butadiene rubber (SSBR 2466) and natural rubber (NR) is characterized by differential scanning calorimetry and dynamic mechanical thermal analysis. The single glass transition (Tg) in the entire temperature range of all NR/SSBR blends and good correlation between Tg and SSBR fraction prove the excellent compatibility between SSBR 2466 and NR. With increasing SSBR content, a reduced Payne effect, more homogeneous dispersion of silica, stronger rubber–filler interaction, and more silica selectively distributed in the SSBR phase were determined via rubber-processing analysis, transmission electron microscopy, bound rubber, and thermogravimetric analysis, respectively. The high vinyl content, low styrene content, and end-functionalized structure of SSBR play vital roles in promoting its compatibility with NR and a stronger rubber–silica linkage. The resulting increased tan δ at 0 °C and low tan δ at 60 °C indicate good wet-skid resistance and low rolling resistance by blending SSBR 2466, and 70/30 NR/SSBR is the best balance for producing a “green tire” tread.