Polyimide/MWCNTs nanocomposites have been fabricated by solution mixing process. In the present study, we have investigated electrical conductivity and dielectric properties of PI/MWCNT nanocomposites in frequency range of 1 kHz to 100 kHz at different MWCNTs concentrations from 0 wt.% to 15 wt.%. It has been observed that the electrical conductivity and dielectric constants are enhanced significantly by several orders of magnitude up to 15 wt.% of MWCNTs content. The electrical conductivity increases as the frequency is increased, which can be attributed to high dislocation density near the interface. The rapid increase in the dielectric constant at a high MWCNTs content can be explained by the formation of a percolative path of the conducting network through the sample for a concentration corresponding to the percolation threshold. The high dielectric constant at a low frequency (1 kHz) is thought to originate from the space charge polarization mechanism. I-V characteristics of these devices indicate a significant increase in current with an increase in multi-walled carbon nanotube concentration in the composites. The SEM images show improved dispersion of MWCNTs in the PI matrix; this is due to the strong interfacial interactions.