Determining the metallicity and semiconductivity of a multi-walled carbon nanotube (MWCNT) bundle plays a particularly vital role in its interconnection with the metal electrode of an integrated circuit. In this paper, an effective method is proposed to determine the electrical transport properties of an MWCNT bundle using a current–voltage characteristic curve during its electrical breakdown. We established the reliable electrical nanoscale contact between the MWCNT bundle and metal electrode using a robotic manipulation system under scanning electron microscope (SEM) vacuum conditions. The experimental results show that the current–voltage curve appears as saw-tooth-like current changes including up and down steps, which signify the conductance and breakdown of carbon shells in the MWCNT bundle, respectively. Additionally, the power law nonlinear behavior of the current–voltage curve indicates that the MWCNT bundle is semiconducting. The molecular dynamics simulation explains that the electron transport between the inner carbon shells, between the outermost carbon shells and gold metal electrode and between the outermost carbons shells of two adjacent individual three-walled carbon nanotubes (TWCNTs) is through their radial deformation. Density functional theory (DFT) calculations elucidate the electron transport mechanism between the gold surface and double-wall carbon nanotube (DWCNT) and between the inner and outermost carbon shells of DWCNT using the charge density difference, electrostatic potential and partial density of states.