Spatially resolved, quantitative, non-destructive analysis using synchrotron x-ray reflectivity (XR) with subnano-scale resolution was successfully performed on the nanoporous organosilicate thin films for low dielectric applications. The structural information of porous thin films, which were prepared with polymethylsilsesquioxane and thermally labile 4-armed, star-shaped poly(ε-caprolactone) (PCL) composites, were characterized in terms of the laterally averaged electron density profile along with a film thickness as well as a total thickness. The thermal process used in this work caused to efficiently undergo sacrificial thermal degradation, generating closed nanopores in the film. The resultant nanoporous films became homogeneous, well-defined structure with a thin skin layer and low surface roughness. The average electron density of the calcined film reduced with increase of the initial porogen loading, and finally leaded to corresponding porosity ranged from 0 to 22.8% over the porogen loading range of 0-30 wt%. In addition to XR analysis, the surface and the inner structures of films are investigated and discussed with atomic force and scanning electron microscopy images.