This work investigates the effect of nanofiber/nets (NFN) on the electrical behaviour of conductive composite nanofibers, using polyethylene oxide (PEO)/multiwall carbon nanotubes (MWCNT) as the model material for the analysis. We demonstrate that water-based solutions, containing high molecular weight PEO and MWCNT can be processed by electrospinning/netting applying high voltages. NFNs are designed with different morphologies, in particular modulating their porosities. A strong enhancement of the electrical conductivity of PEO/MWCNT-NFN is observed for the denser NFN, if compared to nanofiber composites. These results demonstrate that the NFN morphology can directly control the quality of the electron percolation paths. To provide better evidence for this strong dependency we processed the nanocomposite NFN by solvent-induced swelling. This physical mechanism directly modulates the percolation path, tuning the electrical behaviour of the nanocomposites to a resistive one: the better the starting percolation path, the larger the resistivity increase.