The formation of percolation networks in epoxy matrix nanocomposites reinforced with multi-wall carbon nanotubes (MWNT) during the curing process, at different MWNT contents, was studied by using a parallel plate cell subjected to a 300 V/cm AC electric field at 1 kHz. The percolation was verified by the electrical current output measured during and after the resin curing. The behavior of electric dipoles was characterized by impedance spectroscopy and followed the Debye first order dispersion model, by which an average relaxation time of 6.0 x 10(-4) s and a cut-off frequency of 1.7 kHz were experimentally found. By applying the theory of percolation, a critical probability, pc, equal to 0.038 vol% and an exponent of conductivity of 2.0 were found. Both aligned and random samples showed dipole relaxation times typical of interfacial and/or charge-hopping polarization, while the permittivity exhibited an exponential decrease with frequency. This behavior can be related to the increased ability to trap electrical charges due to the formation of the carbon nanotubes network. Optical and electron microscopies confirm the theoretical prediction that the application of an electric field during cure helps the process of MWNT debundling in epoxy resin. (C) 2015 Elsevier B.V. All rights reserved.