The effects of 3 MeV proton irradiation for fluences of 3.5 x 10(10) cm(-2) to 3.1 x 10(12) cm(-2) on structure and electrical conductivity of multi-walled carbon nanotubes (MWCNTs) film were investigated. The pristine and the irradiated MWCNTs films were characterized using scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and electron paramagnetic resonance (EPR) spectroscopy in order to investigate the effects of irradiation on their structure. Electrical conductivity of the MWCNTs films was characterized before and after irradiation. SEM analysis reveals that the proton irradiation for the high fluence (more than 3.6 x 10(11) cm(-2)) leads to evident changes in morphology of the MWCNTs film, such as forming uneven film surface, curve, shrinkage and fragmentation of nanotubes. Based on Raman, XPS, FTIR and EA analyses, it is confirmed that the 3 MeV protons with high fluence (more than 3.6 x 10(11)cm(-2)) can damage the structure of the MWCNTs, including increase of the disorder and the formation of functional groups. EPR spectroscopy shows that the electrons delocalized over carbon nanotubes increase with increasing irradiation fluence, implying that the MWCNTs film might be sensitive to ionizing radiation to some extent. With increasing the irradiation fluence, the electrical conductivity of the MWCNTs film decreases due to the structural and morphological damage. (C) 2014 Elsevier B.V. All rights reserved.