AbstractPreparation and processing of conductive blends based on doped polyaniline (c‐PANI) or tetra‐aniline (c‐TANI) with epoxy resins is described. The dedoping of c‐PANI by the epoxy hardener, in the process of the blend curing, has been investigated by UV–vis–NIR spectroscopy. Classical amine hardeners lead to a quick increase of the blend resistivity during its processing, which can be correlated with the observed spectral features, characteristic of the deprotonation of c‐PANI. For these reasons, for further investigations, BF3‐amine complexes have been selected as curing agents. Using these hardeners and tuning the curing conditions (temperature and time), it is possible to obtain blends with resistivities down to 102 Ω·cm, depending on the type of the epoxy resin used. In general, resins with higher epoxy network densities give c‐PANI‐based blends of lower percolation thresholds. The effect of the c‐PANI processing solvent on the resistivity of the resulting blend is even more pronounced than the epoxy network density. In particular, blends processed from toluene show much higher resistivities than those processed from tetrahydrofuran (THF) of ethylacetate (EA). Above the percolation threshold, c‐TANI‐based epoxy blends show at least three orders of magnitude higher resistivities than their c‐PANI analogues. They are however technologically interesting, because they are not very sensitive to the processing/curing conditions and show lower percolation thresholds. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011