By using the thermally stimulated discharge currents (TSDC) technique and coupling it with the thermal step (TS) method, which allows accurate measurement of the space charge distribution tan outstanding electrical property), both the relaxation and the relative contribution of the intrinsic polarization charges and the extrinsic trapped charges have been analysed for a series of poly(vinyl chloride) (PVC) materials after partial hydrogenation as a precursor structure of polyethylene (PE). The alpha relaxation related to the release of frozen-in dipole orientation, and the rho relaxation which is due to the trapping of extrinsic charges have been found to vary, both in intensity and in temperature, with the percentage of ethylene units. On the other hand, the TS measurement of the space charge distribution prior to and after destroying the polarization charges according to the TSDC behaviour, allows one to correlate, as a first approximation, those types of space charge with the molecular microstructure, of either PVC or PE parts. Even if further work remains to be done, the results, as discussed in the light of earlier work on tacticity-driven microstructure-PVC property relationships and on space charge distribution of PVC after hydrogenation, studied by the TS method, provide an original although still tentative interpretation of the space charge behaviour of PE.