The study presents the possibility of preparation of multi-membrane gel systems with different morphologies and properties, based on poly(N,N-dimethyl-acrylamide-co-3,9-divinyl-2,4,8,10-tetraoxaspiro (5.5) undecane) copolymer and crosslinked with N,N'-methylene-bis-acrylamide. The basic copolymer has dual thermo- and pH sensitive character. After the core hydrogel is realized, the preformed gel is immersed in the aqueous solutions of ammonia, sodium chloride and sodium citrate for further edge constructing of the supramolecular assemblies. Then, the new layers by adding new sets of gelifying components are realized. The new multi-membrane gel systems are intended to be used as matrix for bioactive substances embedding. In this context the systems were loaded with norfloxacin as drug model. The in vivo tests show good biocompatibility for the implants based on multi-membrane gel structures loaded with drug.