Thin films of architectures PEI(CNERa/PDMS)(n), PEI(CNERb/PDMS)(n), (PEI/CNERb)(n) and PEI(CNERb/NH2-MMT/PEI)(n) have been fabricated via covalent layer-by-layer technique. Different film deposition parameters such as solvent type, polymer concentration, polymer ratio and dipping time have been optimized to achieve a uniform growth of layers. The effect of polymer concentration and dipping time on film thickness was also studied via ellipsometer. The optimized ratio of polymer concentration was 1:1 and 1:2 for PEI(CNERa/PDMS)(n) and PEI(CNERb/PDMS)(n), respectively. AFM analysis indicated that the films were homogeneous while contact angle measurements revealed that although films were hydrophobic in nature yet they have wetting property due to the presence of hydroxyl groups formed during curing process. These epoxy-based multilayers have shown significant oil adsorption capacity. All the fabricated films qualify scotch tape test and were found resistant towards strong acids, bases and organic solvents.