Biocompatible polymer blends, such as alginate blends, have a widespread use in pharmaceutical and medical applications due to their specific features, such as biodegradation, adhesiveness, and thermo‐ and pH sensitivity and that can be obtained from the mixture composition. In this work, the use of alginate blends was tested in a novel production methodology of therapeutic dosage forms based on polymeric chain reticulation phenomena induced by exposure to bivalent ions. Two kinds of sodium alginate were used to obtain gel films (structured films) in blends with Pluronic F127®. The blends were considered for applications in gel paving of drug‐eluting stents. Sodium alginate was also used in shell–core particle production (structured particles) to obtain shell‐barrier reducing drug release in the preparative steps (see wash operations). Both structures, films and particles, were obtained using Cu²⁺ and Ca²⁺ ions, respectively. Film/shell barrier properties were tested in dissolution experiments using vitamin B12 as an active molecule model. Experimental work demonstrated that the alginate composition is a crucial point in defining reticulated structures. © 2012 Wiley Periodicals, Inc. Adv Polym Techn 31: 219–230, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/adv.21276