The poly(1,6-heptadiynes) structure induced conductivity was perceived in the range of 534-577 nm corresponding to the 2.2eV mean photon energy absorption via UV-visible spectroscopy. Further the conductivity was realized by investigating AC-conductivity of poly(1,6-heptadiynes) via two-probe measurement enabled impedance spectroscopy. The demonstrated mean frequency independent conductivity was about similar to 3.8*10(-4)S/cm (10(1)-10(7) Hz). Electrospun technique was utilized to fabricate fibrous non-woven mat (0.1w-0.3 wt% of poly(1,6-heptadiynes)) with the aid of engineering thermoplastic Acrylonitrile Butadiene Styrene (ABS) via solution blending, which facilitate the processability and mechanical stability to the poly(1,6-heptadiynes) to accelerate electronic application design. The morphological, conductivity and permittivity measurements were performed on electrospun fibrous non-woven mat. The observed ingenious conductivity was about similar to 1.1*10(-5) S/cm at 10(7)Hz, which was due to enhanced surface area of fibers via electrospinning and poly(1,6-heptadiynes) intrinsic conductivity. Further the conductivity was elucidated by investigating permittivity characteristics. The permittivity results suggest that the diminishing response while adding different poly(1,6-heptadiynes) wt% configurations, which is due to the significant intrinsic conductivity of poly(1,6-heptadiynes). Moreover, the permittivity characteristics 10(3)-10(7) Hz attributes to micro/nanocapacitor Maxwell Wagner Sillars (MWS) and dipolar polarization mechanism.