The electrical properties of polypropylene isomers were correlated with the morphology and chain conformation of differently obtained isotactic (iPP) and syndiotactic (sPP) samples. In the case of iPP, a crystallized and a smectic sample were prepared, whereas for sPP two crystalline helical samples and a mesophase with the chains in trans-planar conformation were considered. The phase composition was obtained for all the samples comparing x-ray diffractograms and transport properties of vapours, which give the crystallinity and the amorphous fraction, respectively. The fraction of mesophase was obtained by the difference of the previous values. The study of the morphology evidenced similarities and differences among the samples, which were discussed and correlated with the phase composition. The electrical conductivity was measured for all the samples, and the syndiotactic isomer showed the lowest value as well as a dependence on the structure. In contrast, the isotactic isomer showed the same behaviour for either polymorph. Based on the structural and electrical results, a phenomenological explanation of the conduction mechanisms taking place in the different forms has been proposed. In particular, the current in the iPP seems to be controlled by Schottky emission, i.e. by field-assisted thermo-ionic injection of carriers from the electrode into the polymer, whereas for the sPP more than one mechanism is likely to be effective, although the ionic transport appears as the predominant one. The experimental data confirm a different behaviour of the ionic conduction properties for the different polymorphs, highlighting the greater insulating characteristics of the mesomorphic structure of the syndiotactic isomer.