In this study, we investigated the kinetic parameters namely, mixing time, the viscosity of the PVDF, aspect ratio of the CNTs and the preparation method influencing the selective distribution of CNTs and thus the viscoelastic, dielectric properties and electrical conductivities of the corresponding (70/30/0.25 w/w/w) PLA/PVDF/CNT nanocomposites. An internal Haake mixer and a twin-screw extruder are used to prepare the nanocomposites. It is found that there is a direct proportionality between formations of a CNT network, rheological responses and conductivities. Moreover, it is revealed that morphology development and CNT localizations are mostly time-dependant mechanism. Nanocomposites prepared in an internal mixer exhibit enhanced conductivities and rheological behaviours owing to the longer mixing time compared to those prepared in an extruder. On the other hand, migration of CNTs from (PVDF+CNT) pre-mixture towards the interface and PLA matrix was retarded in an extruder due to the shorter residence time. Further, viscosity ratio also plays an important role. Low viscous PVDF (L-PVDF) facilitated CNT migrations towards the interface. At last it is found that the highest dielectric permittivity and electrical conductivity is achieved when high aspect ratio CNTs (L-CNT) are pre-mixed with (L-PVDF) for 3 min and mixed with PLA for another 7 min. In contrast, when pre-mixture of high viscous PVDF with low aspect ratio CNT (H-PVDF+S-CNT) is blended with PLA in an extruder the lowest conductivity is obtained resembling those of the insulating materials. It can be stressed that different processing methods and materials characteristics of the same concentrations can yield nanocomposites with different electrical characteristics from insulating to semi-conductive. These findings can provide a new insight into the design and formulation of conductive polymer nanocomposites.