In nanocomposites, the adhesion between nanofillers and the polymeric matrix is key to the mechanical properties. The strength and spatial distribution of the adhesive layer around the nanofillers are important, particularly the presence of chemical bonding between the nanofillers and matrix. In this work, we studied a styrene-butadiene rubber composite filled with silica nanoparticles to visualize the spatial distribution of the adhesive layer. A silane coupling agent (SCA) was added to the nanocomposite for strong adhesion. The reaction involving the SCA on the silica surface was investigated by scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Si-L2,3 spectra of the silica-filled rubber nanocomposite without the SCA were the same around the nanofillers, whereas in the nanocomposite containing the SCA the spectra were position-dependent. The spectra were fitted with the intensity profiles of the Si-L2,3 spectra of silica and SCA by multiple linear least-squares fitting. The fitting coefficients of silica and SCA were used to map the spatial distribution of the chemical bonding between silica and rubber chains. Chemical bonding was observed around the silica nanoparticles but not in the SBR matrix region, providing direct evidence of the reinforcing mechanism in the silica-filled rubber nanocomposite.