Cationic chitosan can form polyionic complexes with anionic polysaccharides such as pectin, which can be cast into films in a similar manner to that of chitosan-starch blends. We report the use of such films as templates in the synthesis of hematite nanoparticles. Mechanistically, the interaction of the iron(II) centers with the carboxyl, amino and other functional groups in the film, after their adsorption into the pores of the template is the key to subsequent synthesis of nanoparticles through calcination. The spatial separation that the specificity of interaction provides is amply made use of through controlled calcination resulting in monodisperse nanoparticles of hematite nanoparticles. This paper also highlights the specific advantages such as rhombohedral shape, similar to 40 nm intensity average diameter, narrow size distribution and weak ferromagnetic properties of using the polyion films at pH 2 as templates over polysaccharides either alone or in combination in solution or as blends. (C) 2012 Elsevier B. V. All rights reserved.