A method to prepare water sensitive composites employing crosslinked poly(vinyl amine) (PVAm) and Cu(II) ions as reticulation agent is disclosed in this work. This article presents in detail, the reticulation reaction and its pH dependence, as well as its electrical, rheological, and thermal properties of the PVAm-Cu(II) composites obtained. The complex bonds formed between the Cu(II) ions and the amine groups of PVAm produce an interesting network of crosslinked structures that generate a microporous morphology when the material is extruded. This characteristic favors fast absorption of water when it is wetted, and a concomitant decrease in its apparent resistivity in a very short period of time. Furthermore, they present an excellent thermal stability and suitable processability. These characteristics make them interesting candidates to design ultra fast water sensors. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 790-801, 2010