Recording SEM images and performing EDX analysis should help if the nanoparticles are made up of high z materials and polymers are made up of low z materials. There will be difference in contrast between the two materials which will be reflected in the EDX images.
But if the nanoparticles are also made up of low z materials similar to that of the polymer i.e., both the nanocomposites and polymer have same contrast then things can get tricky. In such a case, you can get some information based on the surface topography, local ordering etc.
I would suggest fracturing the nanocomposite in liquid nitrogen and trying SEM analysis. if still not good enough, you can try etching the polymer in solvent to get the depth contrast. I hope it helps.