In this paper, we investigate a commercial nematic liquid crystal (LC) mixture namely E7 dispersed with small concentrations of multi-walled carbon nanotubes (MWCNTs). The dielectric and electro-optical characterizations have been carried out in the homogeneously and vertically aligned LC cells. The electro-optical response of LC molecules has been enhanced by 60% after the addition of MWCNTs, which is attributed to the reduced rotational viscosity in the composites. MWCNTs act like barricades for ionic impurities by reducing them up to ∼34.3% within the dispersion limit of 0.05 wt%. The nematic–isotropic phase transition temperature (TNI) of the E7 LC has also been shifted towards the higher temperature, resulting in a more ordered nematic phase. The enhanced birefringence and orientational order parameter in the LC-MWCNTs are attributed to π-π electron stacking between the LC molecules and the MWCNTs. The outlined merits of the LC-MWCNTs composites evince their suitability for ultrafast nematic-based electro-optical devices.