The hierarchical structures of silica-filled silicone rubber have been investigated by using contrast variation small-angle neutron scattering (CV-SANS) and transmission electron microscopy (TEM). A series of scattering intensities of swollen samples were measured with varying ratio of hydrogenated toluene/deuterated toluene solvent. By using CV-SANS method, the partial scattering functions, self-terms of silica S-SS(q) and silicone rubber S-RR(q), as well as cross-term between silica and silicone rubber S-RS(q), are successfully extracted. The fine parameterization of morphology is characterized and elucidated by adopting unified Guinier-exponential/ power-law equations, the fitted results indicate: (i) the volume fraction of silicone rubber in bound rubber and matrix regions, are respectively 0.80 and 0.31. Such spatial inhomogeneous of swelling ratio suggests that there is existence of the immobilized layer; (ii) the average aggregation size is ca. 143 nm, and there are about 24-97 silica particles in each aggregation; (iii) the thickness of the bound rubber is estimated as in the range of ca. 7.2-8.5 nm. A mimic collection and observation of aggregations and bound rubber with TEM confirm the CV-SANS results. Current work provided a scenario to evaluate the reinforcement effect of the silica on the silicone rubber even before any mechanical testing. (C) 2017 Elsevier Ltd. All rights reserved.