Oil-swollen hexagonal mesophases resulting from the surfactant mediated self-assembly of a quaternary mixture of water, surfactant, co-surfactant, and oil, are versatile templates to synthesize anisotropic nanomaterials. Poly(diphenylbutadyine) (PDPB) polymer nanofibrous network structures were produced in the oil tubes of the mesophases by photo-induced radical polymerization using a chemical initiator or by gamma irradiation. The diameter of the nanofibers can be varied from 5 to 25 nm in a controlled fashion, and is directly determined by the diameter of the oil tube of the doped mesophases, proving thus a direct templating effect of the mesophase. The nanoIR technique allows chemical characterization and identification of the polymer nanostructures simultaneously with morphological characterization. Cyclic voltammetry has been used as an effective approach to evaluate both the energy level of the highest occupied molecular orbital (HOMO) as well as the energy of the lowest unoccupied molecular orbital (LUMO) and the band gap of the PDPB. The conductivity of the PDPB nanostructures obtained by gamma irradiation was estimated to be 0.1 S/cm, which is higher than the conductivity of PDPB nanostructures previously reported in the literature. The soft template approach allows size tunable synthesis of anisotropic polymer structures with morphological homogeneity at the nanoscale with high conductivity, thus it appears to be an attractive opportunity for electronic device applications.