Multilayer thin films are useful materials in the fabrication of controlled drug delivery systems and in controlling drug release processes. Herein, we report the step-by-step deposition of polymer multilayers based on poly(ethyleneimine) (PEI) and poly(N-isopropylacrylamide) (PNIPAAm) mediated by pyromellitic dianhydride (PM), as cross-linker of PEI chains, onto Daisogel silica microparticles. The sorption/release properties of the resulting composite microparticles for indomethacin (IDM), diclofenac sodium salt (DS), and Ponceau SS (PSS) were followed as a function of PM concentration. The sorption properties of the [(PEI-PM)/PNIPAAm] n multilayer films for all anionic species (IDM, DS, and PSS) were influenced by the number of polymer layers and the weight ratio between cross-linker and Daisogel microparticles during the cross-linking steps. It was found that the sorbed amount of anionic compounds increased with the number of polymer layers and with the decrease of PM concentration. The Langmuir and Sips model isotherms fitted well the sorption equilibrium data. The maximum equilibrium sorption capacity (q m ) evaluated by the Langmuir model, at 25 C, was 41 mg IDM g À1 of Daisogel//[(PEI-PM)/PNIPAAm] 8.5 and 40 mg PSS g À1 of Daisogel//[(PEI-PM)/PNIPAAm] 8.5 , for a weight percentage of PM/silica of 0.1% w/w. Cumulative release of IDM was faster and higher than PSS in the first 5 h, while PSS was desorbed with a constant rate for 30 h, supporting a sustained release from Daisogel//[(PEI-PM)/PNIPAAm] n composite microparticles.