Purified multi-walled carbon nanotubes (MWCNT) were melt-mixed with poly(vinylidene fluoride) (PVDF), wherein MWCNT concentration was varied from 0.5-5 wt%. Morphological investigation via optical microscopic analysis suggested an increase in MWCNT ‘agglomerate’ size and ‘agglomerate’ size distribution with an increase in MWCNT concentration in PVDF/MWCNT composite. Further, TEM observation revealed the presence of ‘individualized’ as well as ‘agglomerate’ of MWCNT even at 0.5 wt% of MWCNT in the corresponding composite. MWCNT act as a hetero-nucleating agent in these composites, which is manifested by a significant increase in Tc via DSC studies. FTIR spectroscopy and WAXD analysis exhibited an increase in the polar phase (β/γ) associated with PVDF in the corresponding PVDF/MWCNT composites. Moreover, dielectric studies indicated an increase in permittivity beyond 2 wt% MWCNT in PVDF/MWCNT composite, which also showed an electrical percolation threshold between 3-4 wt% MWCNT. In this context, MWCNT were modified with Li-salt of 6, amino hexanoic acid (Li-AHA) to enhance the extent of dispersion of MWCNT in the PVDF matrix and also to increase the interfacial interaction between Li-AHA modified MWCNT and the PVDF chains. An extensive investigation has been carried out to understand the role of Li-AHA modified MWCNT in enhancing the polar phase associated with PVDF.