Polyaniline/multi-walled carbon nanotube (PANI/MWNT) composites were synthesized using in situ polymerization at different aniline/multi-walled carbon nanotube weight ratios (Ani/MWNT = 1/2, 1/1, 2/1 and 3/1) and introduced into an epoxy resin to act as a microwave absorber. The spectroscopic characterization of the process of formation of PANI/MWNT composites were studied using Fourier transform infrared spectroscopy, an ultraviolet-visible spectrophotometer, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron spin resonance. The microwave absorbing properties were investigated by measuring complex permittivity, complex permeability and reflection loss in the 2-18 and 18-40 GHz microwave frequency range, using the free space method. The results showed that the addition of PANI was useful for achieving a large absorption over a wide frequency range, especially for higher frequency values. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.