Poly(ethyleneimine) and poly(4-vinylpyridine) chains adsorbed on Nucleosil silica have been randomly labeled with nitroxide free radicals. The EPR signal is very sensitive to the molecular Brownian motion of the segments and shoves generally at least two different environments: trains adsorbed on the surface with a restricted mobility, and loops and tails protruding into the solution with a fast motion. The rotational correlation times and the relative fraction of each population are given as functions of the coverage achieved and of the specific surface area of the silica for the samples in contact with methanol and sometimes water. The overall picture is consistent with a diffuse layer for the PEI and a more compact one with some heterogeneities for the P4VP.