The objective of this work was to investigate potential interactions between anionic (Eudragit FS) and cationic (Eudragit RL) polymethacrylates of multiple coatings of a novel colonic drug delivery system. Aqueous films of pure polymers Eudragit FS (FS) and Eudragit RL (RL) and their superimposedfilm (FS-RL) were cast on glass slabs. The potential ionic interactions were studied by analysing the dried films using differential scanning calorimetry (DSC), Fourier transform-infrared spectroscopy (FT-IR), and nuclear magnetic resonance (NMR). The glass transition temperatures (Tg) of pure RL and FS were 60 degrees C and 22 degrees C, respectively; FS-RL showed two distinct glass transitions at 59 degrees C and 24 degrees C in the second heating cycle. In the 13C-MAS spectra of the samples in the solid state, no shifts of the resonance could be detected in the superimposed film compared with the pure polymers. The FT-IR spectra of the superimposed film did not show any significant shift of the bands of the -NMe3+ group of RL and the -COO- function of FS compared with the spectra of the pure polymers. No ionic interactions between anionic and cationic polymethacrylates were revealed by DSC, FT-IR, and NMR.